Polymers produced via use of quinolinyldiamido transition metal complexes and vinyl transfer agents

ABSTRACT

Catalyst systems with single site transition metal complexes (such as quinolinyldiamide transition metal complexes), an activator, and a metal hydrocarbenyl transfer agent (preferably an aluminum vinyl-transfer agent) are disclosed for use in alkene polymerization.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of U.S. Ser. No. 62/464,933, filed Feb. 28, 2017 and is incorporated by reference in its entirety.

This application is a Continuation-in-Part of U.S. Ser. No. 15/629,586, filed Jun. 21, 2017, which claims priority to and the benefit of U.S. Ser. No. 62/357,033, filed Jun. 30, 2016.

This application relates to U.S. Ser. No. 62/212,405, filed Aug. 31, 2015; U.S. Ser. No. 62/332,940, filed May 6, 2016; and U.S. Ser. No. 62/332,921, also filed May 6, 2016.

FIELD OF THE INVENTION

The invention relates to the use of quinolinyldiamido transition metal complexes and catalyst systems with an activator and a metal hydrocarbenyl chain transfer agent, such as an aluminum vinyl-transfer agent (AVTA).

BACKGROUND OF THE INVENTION

Pyridyl amines have been used to prepare Group 4 complexes which are useful transition metal components for the polymerization of alkenes, see for example US 2002/0142912; U.S. Pat. Nos. 6,900,321; and 6,103,657, where the ligands have been used in complexes in which the ligands are coordinated in a bidentate fashion to the transition metal atom.

WO 2005/095469 shows catalyst compounds that use tridentate ligands through two nitrogen atoms (one amido and one pyridyl) and one oxygen atom.

US 2004/0220050A1 and WO 2007/067965 disclose complexes in which the ligand is coordinated in a tridentate fashion through two nitrogen (one amido and one pyridyl) and one carbon (aryl anion) donor.

A key step in the activation of these complexes is the insertion of an alkene into the metal-aryl bond of the catalyst precursor (Froese, R. D. J. et al., J. Am. Chem. Soc. 2007, 129, pp. 7831-7840) to form an active catalyst that has both a five-membered and a seven-membered chelate ring.

WO 2010/037059 discloses pyridine containing amines for use in pharmaceutical applications.

U.S. Pat. No. 8,158,733 describes catalyst compositions featuring 2-(2-aryloxy)-8-anilinoquinoline, 2,8-bis(2-aryloxy)quinoline, and 2,8-bis(2-aryloxy)dihydroquinoline ligands that do not feature a tridentate NNN donor ligand.

US 2012/0016092 describes catalyst compositions containing 2-imino-8-anilinoquinoline and 2-aminoalkyl-8-anilinoquinoline ligands having a one-atom linker between the quinoline and the nitrogen donor at the 2-position of the quinoline ring.

US 2010/0227990 A1 discloses ligands that bind to the metal center with a NNC donor set instead of an NNN or NNP donor set.

WO 2002/38628 A2 discloses ligands that bind to the metal center with a NNC donor set instead of an NNN or NNP donor set.

WO 2016/102690 discloses a process for preparation of a branched polyolefin using a metal hydrocarbyl transfer agent.

Organometallics, 2012, 31, p. 3241 by Hu et al. describes catalyst compositions containing 2-aminoalkyl-8-quinolinolato ligands that do not feature a tridentate NNN donor ligand.

Organometallics, 2013, 32, p. 2685 by Nifant'ev et al. describes catalyst compositions containing 2,8-bis(2-aryloxy)dihydroquinoline ligands that do not feature a tridentate NNN donor ligand.

Dalton Transactions, 2013, 42, p. 1501 by Nifant'ev et al. describes catalyst compositions containing 2-aryl-8-arylaminoquinoline ligands that do not feature a tridentate NNN donor ligand.

U.S. Pat. No. 7,858,718 describes catalyst compositions containing 2-aryl-8-anilinoquinoline ligands that do not feature a tridentate NNN donor ligand.

U.S. Pat. No. 7,973,116 describes catalyst compositions containing pyridyldiamide ligands, e.g., a pyridine-based ligand not a quinoline-based ligand.

US 2014/0256893 discloses the use of chain transfer agents, such as diethyl zinc, with transition metal pyridyldiamide catalysts in polymerization processes.

Guerin, F.; McConville, D. H.; Vittal, J. J., Organometallics, 1996, 15, p. 5586, discloses a ligand family and group 4 complexes that use a NNN-donor set, but do not feature seven-membered chelate ring or either of dihydroindenyl- and tetrahydronaphthalenyl-groups.

Macromolecules, 2002, 35, 6760-6762 discloses propene polymerization with tetrakis(pentafluorophenyl)borate, 7-octenyldiisobutylaluminum, and racMe₂Si(2-Me-indenyl)₂ZrCl₂ or Ph₂C(cyclopentadienyl)(fluorenyl)ZrCl₂ to produce polypropylene with octenyldiisobutylaluminum incorporated as a comonomer.

U.S. Pat. Nos. 7,973,116; 8,394,902; US 2011-0224391; US 2011-0301310 A1; and U.S. Ser. No. 61/815,065, filed Apr. 23, 2013, disclose pyridylamido transition metal complexes that do not feature dihydroindenyl- or tetrahydronaphthalenyl-groups.

References of interest also include: 1) Vaughan, A; Davis, D. S.; Hagadorn, J. R. in Comprehensive Polymer Science, Vol. 3, Chapter 20, “Industrial catalysts for alkene polymerization”; 2) Gibson, V. C.; Spitzmesser, S. K. Chem. Rev. 2003, 103, 283; 3) Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. Angew. Chem. Int. Ed. 1999, 38, 428; 4) US 2011/021727; and 5) Zhang, et al., Tetrahedron, Vol. 69, No. 49, Dec. 1, 2013, pages 10644-10652.

There is still a need in the art for new and improved catalyst systems for the polymerization of olefins, in order to achieve specific polymer properties, such as long chain branching, high melting point, high molecular weights, to increase conversion or comonomer incorporation, or to alter comonomer distribution without deteriorating the resulting polymer's properties.

SUMMARY OF THE INVENTION

This invention relates to catalyst systems comprising an activator, metal hydrocarbenyl chain transfer agent (such as an aluminum vinyl-transfer agent), and single site catalyst complex, such as a quinolinyldiamido and related transition metal complexes represented by the Formula (I) or (II):

wherein: M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal; J is a three-atom-length bridge between the quinoline and the amido nitrogen; E is selected from carbon, silicon, or germanium; X is an anionic leaving group; L is a neutral Lewis base; R¹ and R¹³ are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups; R² through R¹² are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino; n is 1 or 2; m is 0, 1, or 2 n+m is not greater than 4; and any two adjacent R groups (e.g., R¹ & R², R² & R³, etc.) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; any two X groups may be joined together to form a dianionic group; any two L groups may be joined together to form a bidentate Lewis base; and an X group may be joined to an L group to form a monoanionic bidentate group.

This invention further relates to catalyst systems comprising activator, transition metal catalyst complex represented by the Formula (I) or (II) above, and aluminum vinyl transfer agent represented by formula: Al(R′)_(3-v)(R″)_(v) wherein each R′, independently, is a C₁-C₃₀ hydrocarbyl group; each R″, independently, is a C₄-C₂₀ hydrocarbenyl group having an end-vinyl group; and v is from 0.1 to 3.

This invention further relates to processes to produce the above catalyst systems and methods to polymerize olefins using the above catalyst systems.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of EP copolymers: wt. % propylene vs. polymer Mn for examples EP-13, 14, 15, 25, 27, 32, 37, 38, 39 (black markers) vs. comparative examples from 2015EM149, EP-13, 15, 17, 19, 22, 23, 25, 27, 29 (gray markers).

FIG. 2 is a graph of EP copolymers: Aluminum vinyl transfer agent (AVTA) concentration in micromoles vs. polymer Mn for examples EP-13 to EP-48 (black markers) vs. comparative examples from 2015EM149, EP-13 to EP-48 (gray markers).

FIG. 3 is a graph of EP copolymers: Aluminum vinyl transfer agent (AVTA) concentration in micromoles vs. polymer g′(vis) from GPC 3D for examples EP-13, 14, 15, 18, 25, 27, 28, 29, 30, 32, 37, 38, 39, 40, 41, 42 from Table 3 (black markers) vs. comparative examples from 2015EM149, EP-15, 17, 19, 22, 23, 25, 27, 29, 35, 39, 43, 45 from table 10 (gray markers).

DETAILED DESCRIPTION OF THE INVENTION

The specification describes transition metal complexes and catalyst systems that include the transition metal complexes. The term complex is used to describe molecules in which an ancillary ligand is coordinated to a central transition metal atom. The ligand is bulky and stably bonded to the transition metal so as to maintain its influence during use of the catalyst, such as polymerization. The ligand may be coordinated to the transition metal by covalent bond and/or electron donation coordination or intermediate bonds. The transition metal complexes are generally subjected to activation to perform their polymerization or oligomerization function using an activator which is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the transition metal.

As used herein, the numbering scheme for the Periodic Table groups is the new notation as set out in Chemical and Engineering News, 63(5), 27 (1985).

“Catalyst productivity” is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T×W) and expressed in units of gPgcat⁻¹ hr⁻¹. Conversion is the amount of monomer that is converted to polymer product, and is reported as mol % and is calculated based on the polymer yield and the amount of monomer fed into the reactor. Catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP/molcat).

An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35 wt % to 55 wt %, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mol % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mol % propylene derived units, and so on. An oligomer is typically a polymer having a low molecular weight, such as an Mn of less than 25,000 g/mol, or in an embodiment less than 2,500 g/mol, or a low number of mer units, such as 75 mer units or less or 50 mer units or less. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mol % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mol % propylene derived units, and so on.

For the purposes of this invention, ethylene shall be considered an α-olefin.

For purposes of this invention and claims thereto, the term “substituted” means that a hydrogen group has been replaced with a heteroatom, or a heteroatom-containing group. For example, a “substituted hydrocarbyl” is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom or heteroatom-containing group.

As used herein, M_(n) is number average molecular weight, M_(w) is weight average molecular weight, and M_(z) is z average molecular weight, wt % is weight percent, and mol % is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined to be M_(w) divided by M_(n). Unless otherwise noted, all molecular weight units (e.g., M_(w), M_(n), M_(z)) are g/mol.

Unless otherwise noted all melting points (Tm) are DSC second melt.

The following abbreviations may be used herein: dme is 1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, cPR is cyclopropyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylalumoxane, p-Me is para-methyl, Ph is phenyl, Bn is benzyl (i.e., CH₂Ph), THF (also referred to as thf) is tetrahydrofuran, RT is room temperature (and is 23° C. unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, Cy is cyclohexyl and AVTA is an aluminum-based vinyl transfer agent.

A “catalyst system” comprises at least one catalyst compound and at least one activator. When “catalyst system” is used to describe such the catalyst compound/activator combination before activation, it means the unactivated catalyst complex (pre-catalyst) together with an activator and, optionally, a co-activator. When it is used to describe the combination after activation, it means the activated complex and the activator or other charge-balancing moiety. The transition metal compound may be neutral as in a pre-catalyst, or a charged species with a counter ion as in an activated catalyst system. For the purposes of this invention and the claims thereto, when catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.

In the description herein, the catalyst may be described as a catalyst precursor, pre-catalyst compound, catalyst compound, transition metal complex, or transition metal compound, and these terms are used interchangeably. A polymerization catalyst system is a catalyst system that can polymerize monomers to polymer. An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. A “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion. Activator and cocatalyst are also used interchangeably.

A scavenger is a compound that is typically added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments a co-activator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound.

Noncoordinating anion (NCA) is defined to mean an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly. The term NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group. An NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon. Activators containing non-coordinating anions can also be referred to as stoichiometric activators. A stoichiometric activator can be either neutral or ionic. The terms ionic activator and stoichiometric ionic activator can be used interchangeably. Likewise, the terms neutral stoichiometric activator and Lewis acid activator can be used interchangeably. The term non-coordinating anion activator includes neutral stoichiometric activators, ionic stoichiometric activators, ionic activators, and Lewis acid activators.

For purposes of this invention and claims thereto in relation to catalyst compounds, the term “substituted” means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom-containing group. For example, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.

For purposes of this invention and claims thereto, “alkoxides” include those where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. In some embodiments, the alkyl group may comprise at least one aromatic group.

The terms “hydrocarbyl radical,” “hydrocarbyl,” “hydrocarbyl group,” “alkyl radical,” and “alkyl” are used interchangeably throughout this document. Likewise, the terms “group,” “radical,” and “substituent” are also used interchangeably in this document. For purposes of this disclosure, “hydrocarbyl radical” is defined to be C1-C100 radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues. Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one halogen (such as Br, Cl, F or I) or at least one functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like, or where at least one heteroatom has been inserted within a hydrocarbyl ring.

The term “alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl radicals may, optionally, be substituted. Examples of suitable alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, 1,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, and the like, including their substituted analogues.

The term “alkoxy” or “alkoxide” means an alkyl ether or aryl ether radical wherein the term alkyl is as defined above. Examples of suitable alkyl ether radicals include, but are not limited to, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxyl, and the like.

The term “aryl” or “aryl group” means a six carbon aromatic ring and the substituted variants thereof, including but not limited to, phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, preferably N, O, or S. As used herein, the term “aromatic” also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics.

Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in the family. Likewise, reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).

The term “ring atom” means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.

A heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylaminophenyl is a heteroatom substituted ring.

The term “continuous” means a system that operates without interruption or cessation. For example, a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.

A solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization is typically homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Such systems are preferably not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res., 29, 2000, 4627.

A bulk polymerization means a polymerization process in which the monomers and/or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A bulk polymerization system contains less than 25 wt % of inert solvent or diluent, preferably less than 10 wt %, preferably less than 1 wt %, preferably 0 wt %.

This invention relates to catalyst systems comprising a quinolinyldiamide transition metal complex represented by the formula (I) or (II), an activator (such as an alumoxane or a non-coordinating anion), and metal hydrocarbenyl transfer agent, typically represented by the formula: Al(R′)_(3-v)(R″)_(v), wherein each R′, independently, is a C₁ to C₃₀ hydrocarbyl group; each R″, independently, is a C₄ to C₂₀ hydrocarbenyl group having an allyl chain end; v is from 0.01 to 3 (such as 1 or 2). Preferably, the metal hydrocarbenyl transfer agent is an aluminum vinyl-transfer agent (AVTA) represented by the formula: Al(R′)_(3-v)(R)_(v) with R defined as a hydrocarbenyl group containing 4 to 20 carbon atoms and featuring an allyl chain end, R′ defined as a hydrocarbyl group containing 1 to 30 carbon atoms, and v defined as 0.1 to 3 (such as 1 or 2).

The catalyst/activator combinations are formed by combining the transition metal complex with activators in any manner known from the literature, including by supporting them for use in slurry or gas phase polymerization. The catalyst/activator combinations may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). The metal hydrocarbenyl transfer agent (preferably an aluminum vinyl transfer agent) may be added to the catalyst and or activator before, during or after the activation of the catalyst complex or before or during polymerization. Typically, the metal hydrocarbenyl transfer agent (preferably the aluminum vinyl-transfer agent) is added to the polymerization reaction separately, such as before, the catalyst/activator pair.

The polymer produced from the polymerization using the catalyst systems described herein preferably contains at least one allyl chain end. Ethylene homopolymers and copolymers are particularly preferred products. If the catalyst complex chosen is also capable of incorporating bulky alkene monomers, such as C₆ to C₂₀ alpha olefins, into the growing polymer chain, then the resulting polymer (typically an ethylene copolymer) may contain long chain branches formed by the insertion of an allyl terminated polymer chain formed in situ (also referred to as a “vinyl-terminated macromonomer”) into the growing polymer chains. Process conditions including residence time, the ratio of monomer to polymer in the reactor, and the ratio of transfer agent to polymer will affect the amount of long chain branching in the polymer, the average length of branches, and the type of branching observed. A variety of branching types may be formed, which include comb architectures and branch on branch structures similar to those found in low-density polyethylene. The combination of chain growth and vinyl-group insertion may lead to polymer with a branched structure and having one or fewer vinyl unsaturations per polymer molecule. The absence of significant quantities of individual polymer molecules containing greater than one vinyl unsaturation prevents or reduces the formation of unwanted crosslinked polymers. Polymers having long chain branching typically have a g′vis of 0.90 or less, alternately 0.85 or less, alternately 0.80 or less, alternately 0.75 or less, alternately 0.70 or less, alternately 0.60 or less.

If the catalyst chosen is poor at incorporating comonomers such as C₂ to C₂₀ alpha olefins, then the polymer obtained is largely linear (little or no long chain branching). Likewise, process conditions including the ratio of transfer agent to polymer will affect the molecular weight of the polymer. Polymers having little or no long chain branching typically have a g′vis of more than 0.90, alternately 0.95 or more, alternately 0.98 or more.

Alkene polymerizations and co-polymerizations using one or more transfer agents, such as an AVTA, with two or more catalysts are also of potential use. Desirable products that may be accessed with this approach includes polymers that have branch block structures and/or high levels of long-chain branching.

The transfer agent to catalyst complex equivalence ratio can be from about 1:100 to 500,000:1. Preferably, the molar ratio of transfer agent to catalyst complex is greater than one. Alternately, the molar ratio of transfer agent to catalyst complex is greater than 30. The AVTA to catalyst complex equivalence ratio can be from about 1:100 to 500,000:1. Preferably, the molar ratio of AVTA to catalyst complex is greater than one. More preferred, the molar ratio of AVTA to catalyst complex is greater than 30.

The AVTA can also be used in combination with other chain transfer agents that are typically used as scavengers, such as trialkyl aluminum compounds (where the alkyl groups are selected from C₁ to C₂₀ alkyl groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof). Usefully, the ATVA can be used in combination with a trialkyl aluminum compound such as tri-n-octylaluminum and triisobutylaluminum.

The transfer agent can also be used in combination with oxygen-containing organoaluminums such as bis(diisobutylaluminum)oxide, MMAO-3A, and other alumoxanes. Certain of these oxygen-containing organoaluminums are expected to serve as scavengers while remaining significantly less prone to hydrocarbyl group chain-transfer than typical organoaluminums, such as trimethylaluminum or tri(n-octyl)aluminum.

The production of di-end-functionalized polymers is possible with this technology. One product, prior to exposure to air, from an alkene polymerization performed in the presence of AVTA is the aluminum-capped species Al(R′)_(3-v)(polymer-CH═CH₂)_(v), where v is 0.1 to 3 (alternately 1 to 3, alternately 1, 2, or 3). The Al-carbon bonds will react with a variety of electrophiles (and other reagents), such as oxygen, halogens, carbon dioxide, and the like. Thus, quenching the reactive polymer mixture with an electrophile prior to exposure to atmosphere would yield a di-end-functionalized product of the general formula: Z-(monomers)_(n)-CH═CH₂, where Z is a group from the reaction with the electrophile and n is an integer, such as from 1 to 1,000,000, alternately from 2 to 50,000, alternately from 10 to 25,000. For example, quenching with oxygen yields a polymer functionalized at one end with a hydroxy group and at the other end with a vinyl group. Quenching with bromine yields a polymer functionalized at one end with a Br group and at the other end with a vinyl group.

Functional group terminated polymers can also be produced using functional group transfer agents (FGTA). In this embodiment of the invention, the FGTA is represented by the formula M^(FGTA)(R′)_(3-v)(FG)_(v), with R′ and v defined as above, M^(FGTA) a group 13 element (such as B or Al), and with FG defined as a group containing 1 to 20 carbon atoms and a functional group Z. The choice of FG is such that it is compatible with the catalyst system being used. Preferred Z groups include, but are not limited to, non-vinyl olefinic groups such as vinylidene, vinylene or trisubstituted olefins, cyclics containing unsaturation such as cyclohexene, cyclooctene, vinyl cyclohexene, aromatics, ethers, and metal-capped alkoxides.

In another embodiment of the invention, the polymer product of this invention are of the formula: polymer-(CH₂)_(n)CH═CH₂ where n is from 2 to 18, preferably from 6 to 14, more preferably 6, and where “polymer” is the attached polymeryl chain. Polymers of this formula are particularly well suited in making branch polymer combs. The polymer combs can be made by any number of methods. One method would be to use a catalyst system to make the vinyl terminated polymer, and then use a second catalyst system to incorporate the vinyl terminated polymer into a polymer backbone made from the second catalyst. This can be done sequentially in one reactor by first making the vinyl terminated polymer and then adding a second catalyst and, optionally, different monomer feeds in the same reactor. Alternatively, two reactors in series can be used where the first reactor is used to make the vinyl terminated polymer which flows into a second reactor in series having the second catalyst and, optionally, different monomer feeds. The vinyl terminated polymer can be a soft material, as in an ethylene propylene copolymer (such as ethylene propylene copolymer rubber), low density polyethylene, or a polypropylene, or a harder material, as in an isotactic polypropylene, high density polyethylene, or other polyethylene. Typically, if the vinyl terminated polymer is soft, it is preferred that the polymer backbone of the comb be hard; if the vinyl terminated polymer is hard, it is preferred that the polymer backbone of the comb be soft; however, any combination of polymer structures and types can be used.

In another embodiment of the invention, the vinyl-terminated polymers (VTPs) of this invention are of formula: polymer-(CH₂)_(n)CH═CH₂ where n is from 2 to 18, preferably from 6 to 14, more preferably 6 to 8, preferably 6 or 8, and where “polymer” is the attached polymeryl chain. VTPs of this formula are particularly well suited in making branch block polymers. The branch block polymers can be made by any number of methods. One method involves using the same catalyst that is used to make the VTP, and then changing polymerization conditions (such as, but not limited to, by changing monomer composition and/or type and/or the amount or presence of AVTA) in the same or different reactor (such as two or more reactors in series). In this case, the branch will have a different polymeric composition vs. the polymer backbone created under the different polymerization conditions. Another method would be to use a catalyst system to make the VTP, then use a second catalyst system to incorporate the VTPs into a polymer backbone made from the second catalyst. This can be done sequentially in one reactor by first making the VTP and then adding a second catalyst and, optionally, different monomer feeds in the same reactor. Alternatively, two reactors in series can be used where the first reactor is used to make the VTP which flows into a second reactor in series having the second catalyst and, optionally, different monomer feeds. The branched block polymers can be of any composition; however, typically, a combination of soft and hard polymers (relative to one another) are preferred. For example, an iPP VTP could be produced in a reactor, and then ethylene added to the existing propylene feed to make a rubber EP that would have iPP branches. Or an iPP VTP could be produced in a first reactor, and then sent to a second reactor containing ethylene (or additional ethylene for a propylene ethylene copolymer and, optionally, additional propylene monomer (and the same or different catalyst) to make a rubber EP that would have iPP branches (or propylene ethylene copolymer branches).

Useful metal hydrocarbenyl transfer agents (preferably the aluminum vinyl transfer agents) are typically present at from 10 or 20 or 50 or 100 equivalents to 600 or 700 or 800 or 1000 equivalents relative to the catalyst complex. Alternately, the metal hydrocarbenyl transfer agents are present at a catalyst complex-to-transfer agent molar ratio of from about 1:3000 to 10:1; alternatively 1:2000 to 10:1; alternatively 1:1000 to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1; alternatively 1:10 to 1:1.

In any embodiment of this invention where the aluminum vinyl transfer agent is present, the aluminum vinyl transfer agent is present at a catalyst complex-to-aluminum vinyl transfer agent molar ratio of from about 1:3000 to 10:1; alternatively 1:2000 to 10:1; alternatively 1:1000 to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1; alternatively 1:10 to 1:1, alternately from 1:1000 or more.

Transition Metal Complex

Transition metal complexes useful herein include quinolinyldiamido transition metal complexes where a three-atom linker is used between the quinoline and the nitrogen donor in the 2-position of the quinoline ring. This has been found to be an important aspect because the use of the three-atom linker is believed to yield a metal complex with a seven-membered chelate ring that is not coplanar with the other five-membered chelate ring. The resulting complex is thought to be effectively chiral (C₁ symmetry), even when there are no permanent stereocenters present. This is a desirable catalyst feature, for example, for the production of isotactic polyolefins.

Transition metal complexes useful herein include quinolinyldiamido transition metal complexes represented by Formula (I), preferably by Formula (II):

wherein: M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal (preferably a group 4 metal); J is group comprising a three-atom-length bridge between the quinoline and the amido nitrogen, preferably a group containing up to 50 non-hydrogen atoms; E is carbon, silicon, or germanium; X is an anionic leaving group, (such as a hydrocarbyl group or a halogen); L is a neutral Lewis base; R¹ and R¹³ are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups; R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, or phosphino; n is 1 or 2; m is 0, 1, or 2, where n+m is not greater than 4; and any two adjacent R groups (e.g., R¹ & R², R² & R³, etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; any two X groups may be joined together to form a dianionic group; any two L groups may be joined together to form a bidentate Lewis base; and any X group may be joined to an L group to form a monoanionic bidentate group.

Preferably, M is a Group 4 metal, such as zirconium or hafnium.

In a preferred embodiment, J is an aromatic substituted or unsubstituted hydrocarbyl (preferably a hydrocarbyl) having from 3 to 30 non-hydrogen atoms, preferably J is represented by the formula:

where R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and E are as defined above, and any two adjacent R groups (e.g., R⁷ & R⁸, R⁸ & R⁹, R⁹ & R¹⁰ & R¹¹, etc.) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms (preferably 5 or 6 atoms), and said ring may be saturated or unsaturated (such as partially unsaturated or aromatic), preferably J is an arylalkyl (such as arylmethyl, etc.) or dihydro-1H-indenyl, or tetrahydronaphthalenyl group.

In embodiments of the invention, J is selected from the following structures:

where

indicates connection to the complex.

In embodiments of the invention, E is carbon.

In embodiments of the invention, X is alkyl (such as alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof), aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, amido (such as NMe₂), or alkylsulfonate.

In embodiments of the invention, L is an ether, amine or thioether.

In embodiments of the invention, R⁷ and R⁸ are joined to form a six-membered aromatic ring with the joined R⁷R⁸ group being —CH═CHCH═CH—.

In embodiments of the invention, R¹⁰ and R¹¹ are joined to form a five-membered ring with the joined R¹⁰R¹¹ group being —CH₂CH₂—.

In embodiments of the invention, R¹⁰ and R¹¹ are joined to form a six-membered ring with the joined R¹⁰R¹¹ group being —CH₂CH₂CH₂—.

In embodiments of the invention, R¹ and R¹³ may be independently selected from phenyl groups that are variously substituted with between zero to five substituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.

In a preferred embodiment of the invention, the quinolinyldiamido transition metal complex represented by the Formula II above where:

M is a Group 4 metal (preferably hafnium);

E is selected from carbon, silicon, or germanium (preferably carbon);

X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, amido, alkoxo, or alkylsulfonate;

L is an ether, amine, or thioether;

R¹ and R¹³ are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups (preferably aryl);

R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;

n is 1 or 2;

m is 0, 1, or 2;

n+m is from 1 to 4; and

two X groups may be joined together to form a dianionic group;

two L groups may be joined together to form a bidentate Lewis base;

an X group may be joined to an L group to form a monoanionic bidentate group;

R⁷ and R⁸ may be joined to form a ring (preferably an aromatic ring, a six-membered aromatic ring with the joined R⁷R⁸ group being —CH═CHCH═CH—);

R¹⁰ and R¹¹ may be joined to form a ring (preferably a five-membered ring with the joined

R¹⁰R¹¹ group being —CH₂CH₂—, a six-membered ring with the joined R¹⁰R¹¹ group being —CH₂CH₂CH₂—).

In embodiments of Formula I and II, R⁴, R⁵, and R⁶ are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R⁴ & R⁵ and/or R⁵ & R⁶) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.

In embodiments of Formula I and II, R⁷, R⁸, R⁹, and R¹⁰ are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R⁷ & R⁸, and/or R⁹ & R¹⁰) may be joined to form a saturated, substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.

In embodiments of Formula I or II, R² and R³ are each, independently, selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R² and R³ may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R² and R³ may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings.

In embodiments of Formula I or II, R¹¹ and R¹² are each, independently, selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R¹¹ and R¹² may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R¹¹ and R¹² may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings.

In embodiments of Formula I or II, R¹ and R¹³ may be independently selected from phenyl groups that are variously substituted with between zero to five substituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.

In embodiments of Formula II, preferred R¹²-E-R¹¹ groups include CH₂, CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂, Si(alkyl)₂, CH(aryl), CH(Ph), CH(alkyl), and CH(2-isopropylphenyl), where alkyl is a C₁ to C₄₀ alkyl group (preferably C₁ to C₂₀ alkyl, preferably one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is a C₅ to C₄₀ aryl group (preferably a C₆ to C₂₀ aryl group, preferably phenyl or substituted phenyl, preferably phenyl, 2-isopropylphenyl, or 2-tertbutylphenyl).

Preferably, the R groups above and other R groups mentioned hereafter, contain from 1 to 30, preferably 2 to 20 carbon atoms, especially from 6 to 20 carbon atoms.

Preferably, M is Ti, Zr, or Hf, and E is carbon, with Zr or Hf based complexes being especially preferred.

In any embodiment described herein, E is carbon and R¹² and R¹¹ are independently selected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyl groups with from one to ten carbons.

In any embodiment described herein of Formula II, R¹¹ and R¹² are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl.

In any embodiment described herein of Formula II, R⁷, R⁸, R⁹, and R¹⁰ are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, and trimethylsilyl.

In any embodiment described herein of Formula I or II, R², R³, R⁴, R⁵, and R⁶ are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.

In any embodiment described herein of Formula I or II, each L is independently selected from Et₂O, MeOtBu, Et₃N, PhNMe₂, MePh₂N, tetrahydrofuran, and dimethylsulfide.

In any embodiment described herein of Formula I or II, each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

In any embodiment described herein of Formula I or II, R¹ is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

In any embodiment described herein of Formula I or II, R¹³ is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

In any embodiment described herein of Formula II, wherein J is dihydro-1H-indenyl and R¹ is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

In any embodiment described herein of Formula I or II, R¹ is 2,6-diisopropylphenyl and R¹³ is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.

In another aspect of the invention there are provided various processes for synthesizing the complexes described herein.

Ligand Synthesis

The quinolinyldiamine ligands described herein are generally prepared in multiple steps. The main step in the synthesis of the quinolinyldiamine ligand is the carbon-carbon bond coupling step shown below in Scheme 1, wherein fragment 1 and fragment 2 are joined together in a transition metal mediated reaction. In the specific examples described herein the coupling step involves the use of Pd(PPh₃)₄, but other transition metal catalysts (e.g., Ni or Cu containing complexes) are also useful for this type of coupling reaction. In the specific examples described herein, the W* and Y* groups used were a boronic acid ester and a halide, respectively. This choice was suitable for the Pd-mediated coupling step, but other groups may also be useful for the coupling reaction. Other possible W* and Y* groups of interest include alkali metal (e.g., Li), alkaline earth metal halide (e.g., MgBr), zinc halide (e.g., ZnCl), zincate, halide, and triflate. In Scheme 1, R¹ through R¹³ and E are as described above.

One method for the preparation of transition metal quinolinyldiamide complexes is by reaction of the quinolinyldiamine ligand with a metal reactant containing anionic basic leaving groups. Typical anionic basic leaving groups include dialkylamido, benzyl, phenyl, hydrido, and methyl. In this reaction, the role of the basic leaving group is to deprotonate the quinolinyldiamine ligand. Suitable metal reactants for this type of reaction include, but are not limited to, HfBn₄ (Bn=CH₂Ph), ZrBn₄, TiBn₄, ZrBn₂Cl₂(OEt₂), HfBn₂Cl₂(OEt₂)₂, Zr(NMe₂)₂Cl₂(dimethoxyethane), Hf(NMe₂)₂Cl₂(dimethoxyethane), Hf(NMe₂)₄, Zr(NMe₂)₄, and Hf(NEt₂)₄. In the specific examples presented herein Hf(NMe₂)₄ is reacted with a quinolinyldiamine ligand at elevated temperatures to form the quinolinyldiamide complex with the formation of two molar equivalents of dimethylamine, which is lost or removed before the quinolinyldiamide complex is isolated.

A second method for the preparation of transition metal quinolinyldiamide complexes is by reaction of the quinolinyldiamine ligand with an alkali metal or alkaline earth metal base (e.g., BuLi, EtMgBr) to deprotonate the ligand, followed by reaction with a metal halide (e.g., HfCl₄, ZrCl₄).

Quinolinyldiamide (QDA) metal complexes that contain metal-halide, alkoxide, or amido leaving groups may be alkylated by reaction with organolithium, Grignard, and organoaluminum reagents as shown in Scheme 2. In the alkylation reaction the alkyl groups are transferred to the QDA metal center and the leaving groups are removed. In Scheme 2, R¹ through R¹³ and E are as described above and X* is a halide, alkoxide, or dialkylamido leaving group. Reagents typically used for the alkylation reaction include, but are not limited to, MeLi, MeMgBr, Me₂Mg, AlMe₃, AliBu₃, AlOct₃, and PhCH₂MgCl. Typically 2 to 20 molar equivalents of the alkylating reagent are added to the QDA complex. The alkylations are generally performed in ethereal or hydrocarbon solvents or solvent mixtures at temperatures typically ranging from −80° C. to 70° C.

In a preferred embodiment of the invention, the transition metal complex is not a metallocene. A metallocene catalyst is defined as an organometallic compound with at least one e-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two n-bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties.

Activators

The catalyst systems typically comprise a transition metal complex as described above and an activator such as alumoxane or a non-coordinating anion. Activation may be performed using alumoxane solution including methyl alumoxane, referred to as MAO, as well as modified MAO, referred to herein as MMAO, containing some higher alkyl groups to improve the solubility. Particularly useful MAO can be purchased from Albemarle, typically in a 10 wt % solution in toluene. The catalyst system employed in the present invention may use an activator selected from alumoxanes, such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane, iso-butyl alumoxane, and the like.

When an alumoxane or modified alumoxane is used, the complex-to-activator molar ratio is from about 1:3000 to 10:1; alternatively 1:2000 to 10:1; alternatively 1:1000 to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1; alternatively 1:10 to 1:1. When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator at a 5000-fold molar excess over the catalyst precursor (per metal catalytic site). The preferred minimum activator-to-complex ratio is 1:1 molar ratio.

Activation may also be performed using non-coordinating anions, referred to as NCA's, of the type described in EP 277 003 Al and EP 277 004 Al. NCA may be added in the form of an ion pair using, for example, [DMAH]+[NCA]- in which the N,N-dimethylanilinium (DMAH) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]-. The cation in the precursor may, alternatively, be trityl. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, such as B(C₆F5)₃, which abstracts an anionic group from the complex to form an activated species. Useful activators include N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate (i.e., [PhNMe₂H]B(C₆F5)₄) and N,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph is phenyl, and Me is methyl.

Additionally preferred activators useful herein include those described in U.S. Pat. No. 7,247,687 at column 169, line 50 to column 174, line 43, particularly column 172, line 24 to column 173, line 53.

In an embodiment of the invention described herein, the non-coordinating anion activator is represented by the following formula (1): (Z)_(d) ⁺(A^(d−))  (1) wherein Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen and (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3.

When Z is (L-H) such that the cation component is (L-H)d⁺, the cation component may include Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the catalyst precursor, resulting in a cationic transition metal species, or the activating cation (L-H)d₊ is a Bronsted acid, capable of donating a proton to the catalyst precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, or ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such as dimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniums from thioethers, such as diethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid, it may be represented by the formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, or a C₁ to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by the formula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with a heteroatom, and/or a C₁ to C₄₀ hydrocarbyl. In an embodiment, the reducible Lewis acid is triphenyl carbenium.

Embodiments of the anion component Ad⁻ include those having the formula [Mk+Qn]d⁻ wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6, or 3, 4, 5, or 6; n-k=d; M is an element selected from Group 13 of the Periodic Table of the Elements, or boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than one occurrence is Q a halide, and two Q groups may form a ring structure. Each Q may be a fluorinated hydrocarbyl radical having 1 to 20 carbon atoms, or each Q is a fluorinated aryl radical, or each Q is a pentafluoryl aryl radical. Examples of suitable Ad⁻ components also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.

In an embodiment in any of the NCA's represented by Formula 1 described above, the anion component Ad⁻ is represented by the formula [M*k*+Q*n*]d*- wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or 6 (or 1, 2, 3, or 4); n*-k*=d*; M* is boron; and Q* is independently selected from hydride, bridged or unbridged dialkylamido, halogen, alkoxide, aryloxide, hydrocarbyl radicals, said Q* having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q* a halogen.

This invention also relates to a method to polymerize olefins comprising contacting olefins (such as propylene) with a catalyst complex as described above and an NCA activator represented by the Formula (2): R_(n)M**(ArNHaI)_(4-n)  (2) where R is a monoanionic ligand; M** is a Group 13 metal or metalloid; ArNHaI is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring, or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; and n is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 2 also comprises a suitable cation that is essentially non-interfering with the ionic catalyst complexes formed with the transition metal compounds, or the cation is Z_(d) ⁺ as described above.

In an embodiment in any of the NCA's comprising an anion represented by Formula 2 described above, R is selected from the group consisting of C₁ to C₃₀ hydrocarbyl radicals. In an embodiment, C₁ to C₃₀ hydrocarbyl radicals may be substituted with one or more C₁ to C₂₀ hydrocarbyl radicals, halide, hydrocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, arylphosphide, or other anionic substituent; fluoride; bulky alkoxides, where bulky means C₄ to C₂₀ hydrocarbyl radicals; —SRa, —NRa₂, and —PRa₂, where each Ra is independently a monovalent C₄ to C₂₀ hydrocarbyl radical comprising a molecular volume greater than or equal to the molecular volume of an isopropyl substitution or a C₄ to C₂₀ hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to the molecular volume of an isopropyl substitution.

In an embodiment in any of the NCA's comprising an anion represented by Formula 2 described above, the NCA also comprises cation comprising a reducible Lewis acid represented by the formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, and/or a C₁ to C₄₀ hydrocarbyl, or the reducible Lewis acid represented by the formula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with one or more heteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an embodiment in any of the NCA's comprising an anion represented by Formula 2 described above, the NCA may also comprise a cation represented by the formula, (L-H)d⁺, wherein L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or (L-H)d⁺ is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S. Pat. Nos. 7,297,653 and 7,799,879, which are fully incorporated by reference herein.

In an embodiment, an activator useful herein comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the Formula (3): (OX^(e+))_(d)(A^(d−))_(e)  (3) wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; e is 1, 2, or 3; d is 1, 2, or 3; and A^(d−) is a non-coordinating anion having the charge of d− (as further described above). Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Suitable embodiments of A^(d−) include tetrakis(pentafluorophenyl)borate.

Activators useful in catalyst systems herein include: trimethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, and the types disclosed in U.S. Pat. No. 7,297,653, which is fully incorporated by reference herein.

Suitable activators also include: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph₃C+][B(C₆F₅)₄—], [Me₃NH+][B(C₆F₅)₄—]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium; and tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In an embodiment, the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In an embodiment, two NCA activators may be used in the polymerization and the molar ratio of the first NCA activator to the second NCA activator can be any ratio. In an embodiment, the molar ratio of the first NCA activator to the second NCA activator is 0.01:1 to 10,000:1, or 0.1:1 to 1000:1, or 1:1 to 100:1.

In an embodiment of the invention, the NCA activator-to-catalyst ratio is a 1:1 molar ratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1 or 1:1 to 1000:1. In an embodiment, the NCA activator-to-catalyst ratio is 0.5:1 to 10:1, or 1:1 to 5:1.

In an embodiment, the catalyst compounds can be combined with combinations of alumoxanes and NCA's (see for example, U.S. Pat. Nos. 5,153,157; 5,453,410; EP 0 573 120 B1; WO 94/07928; and WO 95/14044 which discuss the use of an alumoxane in combination with an ionizing activator, all of which are incorporated by reference herein).

In a preferred embodiment of the invention, when an NCA (such as an ionic or neutral stoichiometric activator) is used, the complex-to-activator molar ratio is typically from 1:10 to 1:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2.

Alternately, a co-activator or chain transfer agent, such as a group 1, 2, or 13 organometallic species (e.g., an alkyl aluminum compound such as tri-n-octyl aluminum), may also be used in the catalyst system herein. The complex-to-co-activator molar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

Metal Hydrocarbenyl Transfer Agents (Aluminum Vinyl Transfer Agents)

The catalyst systems described herein further comprise a metal hydrocarbenyl transfer agent (which is any group 12 or 13 metal agent that contains at least one transferrable group that has an allyl chain end), preferably an aluminum vinyl-transfer agent, also referred to as an AVTA, (which is any aluminum agent that contains at least one transferrable group that has an allyl chain end). An allyl chain end is represented by the formula H₂C═CH—CH₂—. “Allylic vinyl group,” “allyl chain end,” “vinyl chain end,” “vinyl termination,” “allylic vinyl group,” “terminal vinyl group,” and “vinyl terminated” are used interchangeably herein and refer to an allyl chain end. An allyl chain end is not a vinylidene chain end or a vinylene chain end. The number of allyl chain ends, vinylidene chain ends, vinylene chain ends, and other unsaturated chain ends is determined using ¹H NMR at 120° C. using deuterated tetrachloroethane as the solvent on an at least 250 MHz NMR spectrometer.

Useful transferable groups containing an allyl chain end are represented by the formula CH₂═CH—CH₂—R*, where R* represents a hydrocarbyl group or a substituted hydrocarbyl group, such as a C₁ to C₂₀ alkyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof.

In the catalyst system described herein, the catalyst undergoes alkyl group transfer with the transfer agent, which enables the formation of polymer chains containing one or more allyl chain ends.

Useful transferable groups containing an allyl chain end also include those represented by the formula CH₂═CH—CH₂—R**, where R** represents a hydrocarbeneyl group or a substituted hydrocarbeneyl group, such as a C₁ to C₂₀ alkylene, preferably methylene (CH₂), ethylene [(CH₂)₂], propandiyl [(CH₂)₃], butandiyl [(CH₂)₄], pentandiyl [(CH₂)₅], hexandiyl [(CH₂)₆], heptandiyl [(CH₂)₇], octandiyl [(CH₂)₈], nonandiyl [(CH₂)₉], decandiyl [(CH₂)₁₀], undecandiyl [(CH₂₀)₁₁], dodecandiyl [(CH₂)₁₂], or an isomer thereof. Useful transferable groups are preferably non-substituted linear hydrocarbeneyl groups. Preferably, at least one R** is a C₄-C₂₀ hydrocarbenyl group.

The term “hydrocarbeneyl” refers to a hydrocarb-di-yl divalent group, such as a C₁ to C₂₀ alkylene (i.e., methylene (CH₂), ethylene [(CH₂)₂], propandiyl [(CH₂)₃], butandiyl [(CH₂)₄], pentandiyl [(CH₂)₅], hexandiyl [(CH₂)₆], heptandiyl [(CH₂)₇], octandiyl [(CH₂)₈], nonandiyl [(CH₂)₉], decandiyl [(CH₂)₁₀], undecandiyl [(CH₂)₁₁₁], dodecandiyl [(CH₂)₁₂], and isomers thereof).

AVTA's are alkenylaluminum reagents capable of causing group exchange between the transition metal of the catalyst system (M^(TM)) and the metal of the AVTA (M^(AVTA)). The reverse reaction may also occur such that the polymeryl chain is transferred back to the transition metal of the catalyst system. This reaction scheme is illustrated below:

wherein M^(TM) is an active transition metal catalyst site and P is the polymeryl chain, M^(AVTA) is the metal of the AVTA, and R is a transferable group containing an allyl chain end, such as a hydrocarbyl group containing an allyl chain end, also called a hydrocarbenyl or alkenyl group.

Catalyst systems of this invention preferably have high rates of olefin propagation and negligible or no chain termination via beta hydride elimination, beta methyl elimination, or chain transfer to monomer relative to the rate of chain transfer to the AVTA or other chain transfer agent, such as an aluminum alkyl, if present. Quinolinyldiamido catalyst complexes (see U.S. Ser. No. 62/357,033, filed Jun. 30, 2016) and/or other catalyst compounds (U.S. Pat. Nos. 7,973,116; 8,394,902; 8,674,040; 8,710,163; 9,102,773; US 2014/0256893; US 2014/0316089; and US 2015/0141601) activated with non-coordinating activators such as dimethylanilinium tetrakis(perfluorophenyl)borate and/or dimethylanilinium tetrakis(perfluoronaphthyl)borate are particularly useful in the catalyst systems of this invention. Compound 3, described above is particularly preferred.

In any embodiment of the invention described herein, the catalyst system comprises an aluminum vinyl transfer agent, which is typically represented by the formula (A): Al(R′)_(3-v)(R)_(v) where R is a hydrocarbenyl group containing 4 to 20 carbon atoms having an allyl chain end, R′ is a hydrocarbyl group containing 1 to 30 carbon atoms, and v is 0.1 to 3, alternately 1 to 3, alternately 1.1 to less than 3, alternately v is 0.5 to 2.9, 1.1 to 2.9, alternately 1.5 to 2.7, alternately 1.5 to 2.5, alternately 1.8 to 2.2. The compounds represented by the formula Al(R′)_(3-v)(R)_(v) are typically a neutral species, but anionic formulations may be envisioned, such as those represented by formula (B): [Al(R′)_(4-w)(R)_(w)]⁻, where w is 0.1 to 4, R is a hydrocarbenyl group containing 4 to 20 carbon atoms having an allyl chain end, and R′ is a hydrocarbyl group containing 1 to 30 carbon atoms.

In any embodiment of any formula for a metal hydrocarbenyl transfer agent, such as formula A or B, described herein, each R′ is independently chosen from C₁ to C₃₀ hydrocarbyl groups (such as a C₁ to C₂₀ alkyl groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof), and R is represented by the formula: —(CH₂)_(n)CH═CH₂ where n is an integer from 2 to 18, preferably 6 to 18, preferably 6 to 12, preferably 6.

In any embodiment of the invention described herein, particularly useful AVTAs include, but are not limited to, tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, diisobutyl(dodec-11-en-1-yl)aluminum, and the like. Mixtures of one or more AVTAs may also be used. In some embodiments of the invention, isobutyl-di(oct-7-en-1-yl)-aluminum, isobutyl-di(dec-9-en-1-yl)-aluminum, isobutyl-di(non-8-en-1-yl)-aluminum, isobutyl-di(hept-6-en-1-yl)-aluminum are preferred.

Particularly useful metal hydrocarbenyl transfer agents comprises one or more of tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, dimethyl(dec-9-en-1-yl)aluminum, diethyl(dec-9-en-1-yl)aluminum, dibutyl(dec-9-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, and diisobutyl(dodec-11-en-1-yl)aluminum.

Useful aluminum vinyl transfer agents include organoaluminum compound reaction products between aluminum reagent (AlR^(a3)) and an alkyl diene. Suitable alkyl dienes include those that have two “alpha olefins”, as described above, at two termini of the carbon chain. The alkyl diene can be a straight chain or branched alkyl chain and substituted or unsubstituted. Exemplary alkyl dienes include but are not limited to, for example, 1,3-butadiene, 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene, 1,17-octadecadiene, 1,18-nonadecadiene, 1,19-eicosadiene, 1,20-heneicosadiene, etc. Exemplary aluminum reagents include triisobutylaluminum, diisobutylaluminumhydride, isobutylaluminumdihydride and aluminum hydride (AlH₃).

In any embodiment of the invention described herein, R″ is butenyl, pentenyl, heptenyl, octenyl or decenyl. In some embodiments R″ is preferably octenyl or decenyl.

In any embodiment of the invention described herein, R′ is methyl, ethyl, propyl, isobutyl, or butyl. In any embodiment of the invention described herein, R′ is isobutyl.

In any embodiment of the invention described herein, v is about 2, or v is 2.

In any embodiment of the invention described herein, v is about 1, or v is 1, preferably from about 1 to about 2.

In any embodiment of the invention described herein, v is an integer or a non-integer, preferably v is from 1.1 to 2.9, from about 1.5 to about 2.7, e.g., from about 1.6 to about 2.4, from about 1.7 to about 2.4, from about 1.8 to about 2.2, from about 1.9 to about 2.1 and all ranges there between.

In preferred embodiments of the invention described herein, R′ is isobutyl and each R″ is octenyl or decenyl, preferably R′ is isobutyl, each R″ is octenyl or decenyl, and v is from 1.1 to 2.9, from about 1.5 to about 2.7, e.g., from about 1.6 to about 2.4, from about 1.7 to about 2.4, from about 1.8 to about 2.2, from about 1.9 to about 2.1.

The amount of v (the aluminum alkenyl) is described using the formulas: (3-v)+v=3, and Al(R′)_(3-v)(R″)_(v) where R″ is a hydrocarbenyl group containing 4 to 20 carbon atoms having an allyl chain end, R′ is a hydrocarbyl group containing 1 to 30 carbon atoms, and v is 0.1 to 3 (preferably 1.1 to 3). This formulation represents the observed average of organoaluminum species (as determined by ¹H NMR) present in a mixture, which may include any of Al(R′)₃, Al(R′)₂(R″), Al(R′)(R″)₂, and Al(R″)₃. ¹H NMR spectroscopic studies are performed at room temperature using a Bruker 400 MHz NMR. Data is collected using samples prepared by dissolving 10-20 mg the compound in 1 mL of C₆D₆. Samples are then loaded into 5 mm NMR tubes for data collection. Data is recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging either 8 or 16 transients. The spectra are normalized to protonated tetrachloroethane in the C₆D₆. The chemical shifts (6) are reported as relative to the residual protium in the deuterated solvent at 7.15 ppm.

In still another aspect, the aluminum vinyl-transfer agent has less than 50 wt % dimer present, based upon the weight of the AVTA, preferably less than 40 wt %, preferably less than 30 wt %, preferably less than 20 wt %, preferably less than 15 wt %, preferably less than 10 wt %, preferably less than 5 wt %, preferably less than 2 wt %, preferably less than 1 wt %, preferably 0 wt % dimer. Alternately dimer is present at from 0.1 to 50 wt %, alternately 1 to 20 wt %, alternately at from 2 to 10 wt %. Dimer is the dimeric product of the alkyl diene used in the preparation of the AVTA. The dimer can be formed under certain reaction conditions, and is formed from the insertion of a molecule of diene into the Al—R bond of the AVTA, followed by beta-hydride elimination. For example, if the alkyl diene used is 1,7-octadiene, the dimer is 7-methylenepentadeca-1,14-diene. Similarly, if the alkyl diene is 1,9-decadiene, the dimer is 9-methylenenonadeca-1,18-diene.

Useful compounds can be prepared by combining an aluminum reagent (such as alkyl aluminum) having at least one secondary alkyl moiety (such as triisobutylaluminum) and/or at least one hydride, such as a dialkylaluminum hydride, a monoalkylaluminum dihydride or aluminum trihydride (aluminum hydride, AlH₃) with an alkyl diene and heating to a temperature that causes release of an alkylene byproduct. The use of solvent(s) is not required. However, non-polar solvents can be employed, such as, as hexane, pentane, toluene, benzene, xylenes, and the like, or combinations thereof.

In an embodiment of the invention, the AVTA is free of coordinating polar solvents such as tetrahydrofuran and diethylether.

After the reaction is complete, solvent if, present can be removed and the product can be used directly without further purification.

The AVTA to catalyst complex equivalence ratio can be from about 1:100 to 500,000:1. More preferably, the molar ratio of AVTA to catalyst complex is greater than 5, alternately greater than 10, alternately greater than 15, alternately greater than 20, alternately greater than 25, alternately greater than 30.

In another embodiment of the invention, the metal hydrocarbenyl transfer agent is an alumoxane formed from the hydrolysis of the AVTA. Alternatively, the alumoxane can be formed from the hydrolysis of the AVTA in combination with other aluminum alkyl(s). The alumoxane component is an oligomeric compound which is not well characterized, but can be represented by the general formula (R—Al—O)_(m) which is a cyclic compound, or may be R′(R—Al—O)_(m)—AlR′₂ which is a linear compound where R′ is as defined above and at least one R′ is the same as R (as defined above), and m is from about 4 to 25, with a range of 13 to 25 being preferred. Most preferably all R′ are R. An alumoxane is generally a mixture of both the linear and cyclic compounds.

Supports

The complexes described herein may be supported (with or without an activator and with or without a transfer agent) by any method effective to support other coordination catalyst systems, effectively meaning that the catalyst so prepared can be used for polymerizing olefin(s) in a heterogeneous process. The catalyst precursor, activator, optional transfer agent, co-activator if needed, suitable solvent, and support may be added in any order or simultaneously. Typically, the complex, activator, and optional transfer agent may be combined in solvent to form a solution. Then the support is added, and the mixture is stirred for 1 minute to 10 hours. The total solution volume may be greater than the pore volume of the support, but some embodiments limit the total solution volume below that needed to form a gel or slurry (about 90% to 400%, preferably about 100% to 200% of the pore volume). After stirring, the residual solvent is removed under vacuum, typically at ambient temperature and over 10-16 hours. But greater or lesser times and temperatures are possible.

The complex may also be supported absent the activator, and in that case, the activator (and co-activator if needed) is added to a polymerization process' liquid phase. Additionally, two or more different complexes may be placed on the same support. Likewise, two or more activators or an activator and co-activator may be placed on the same support. Likewise the transfer agent may be added to the polymerization reaction separately from the supported catalyst complex and/or activator.

Suitable solid particle supports are typically comprised of polymeric or refractory oxide materials, each being preferably porous. Preferably, any support material that has an average particle size greater than 10 μm is suitable for use in this invention. Various embodiments select a porous support material, such as for example, talc, inorganic oxides, inorganic chlorides, for example magnesium chloride and resinous support materials such as polystyrene polyolefin or polymeric compounds or any other organic support material and the like. Some embodiments select inorganic oxide materials as the support material including Group-2, -3, -4, -5, -13, or -14 metal or metalloid oxides. Some embodiments select the catalyst support materials to include silica, alumina, silica-alumina, and their mixtures. Other inorganic oxides may serve either alone or in combination with the silica, alumina, or silica-alumina. These are magnesia, titania, zirconia, and the like. The support can optionally double as the activator component; however, an additional activator may also be used.

The support material may be pre-treated by any number of methods. For example, inorganic oxides may be calcined, chemically treated with dehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordance with the invention, see, for example, the descriptions in WO 95/15815 and U.S. Pat. No. 5,427,991. The methods disclosed may be used with the catalyst complexes, activators or catalyst systems of this invention to adsorb or absorb them on the polymeric supports, particularly if made up of porous particles, or may be chemically bound through functional groups bound to or in the polymer chains.

Useful supports typically have a surface area of from 10-700 m²/g, a pore volume of 0.1-4.0 cc/g and an average particle size of 10-500 μm. Some embodiments select a surface area of 50-500 m2/g, a pore volume of 0.5-3.5 cc/g, or an average particle size of 20-200 am. Other embodiments select a surface area of 100-400 m2/g, a pore volume of 0.8-3.0 cc/g, and an average particle size of 30-100 μm. Useful supports typically have a pore size of 10-1000 Angstroms, alternatively 50-500 Angstroms, or 75-350 Angstroms.

The catalyst complexes described herein are generally deposited on the support at a loading level of 10-100 micromoles of complex per gram of solid support; alternately 20-80 micromoles of complex per gram of solid support; or 40-60 micromoles of complex per gram of support. But greater or lesser values may be used provided that the total amount of solid complex does not exceed the support's pore volume.

Polymerization

Invention catalyst complexes are useful in polymerizing unsaturated monomers conventionally known to undergo coordination-catalyzed polymerization such as solution, slurry, gas-phase, and high-pressure polymerization. Typically, one or more of the complexes described herein, one or more activators, one or more transfer agents (such as an aluminum vinyl transfer agent) and one or more monomers are contacted to produce polymer. The complexes may be supported and, as such, will be particularly useful in the known, fixed-bed, moving-bed, fluid-bed, slurry, gas phase, solution, or bulk operating modes conducted in single, series, or parallel reactors.

One or more reactors in series or in parallel may be used in the present invention.

The complexes, activator, transfer agent, and, when required, co-activator, may be delivered as a solution or slurry, either separately to the reactor, activated in-line just prior to the reactor, or pre-activated and pumped as an activated solution or slurry to the reactor. Polymerizations are carried out in either single reactor operation, in which monomer, comonomers, catalyst/activator/co-activator, optional scavenger, and optional modifiers are added continuously to a single reactor or in series reactor operation, in which the above components are added to each of two or more reactors connected in series. The catalyst components can be added to the first reactor in the series. The catalyst component may also be added to both reactors, with one component being added to the first reaction and another component to other reactors. In one preferred embodiment, the complex is activated in the reactor in the presence of olefin and transfer agent.

In a particularly preferred embodiment, the polymerization process is a continuous process.

Polymerization process used herein typically comprises contacting one or more alkene monomers with the complexes, activators and transfer agents described herein. For purpose of this invention alkenes are defined to include multi-alkenes (such as dialkenes) and alkenes having just one double bond. Polymerization may be homogeneous (solution or bulk polymerization) or heterogeneous (slurry—in a liquid diluent, or gas phase—in a gaseous diluent). In the case of heterogeneous slurry or gas phase polymerization, the complex and activator may be supported. Silica is useful as a support herein. Chain transfer agents (such as hydrogen or trialkylaluminums) may be used in the practice of this invention.

The present polymerization processes may be conducted under conditions preferably including a temperature of about 30° C. to about 200° C., preferably from 60° C. to 195° C., preferably from 75° C. to 190° C. The process may be conducted at a pressure of from 0.05 to 1500 MPa. In a preferred embodiment, the pressure is between 1.7 MPa and 30 MPa, or in another embodiment, especially under supercritical conditions, the pressure is between 15 MPa and 1500 MPa.

If branching (such as a g′vis of less than 0.90) is desired in the polymer product, then, among other things, one may increase the concentration of the metal hydrocarbenyl transfer agent, increase the temperature of the polymerization reaction, increase the solids content in the polymerization reaction mass (i.e., increase the solids content) or increase the residence time of the polymerization. Likewise if a more linear polymer is desired, then then, among other things, one may reduce the concentration of the metal hydrocarbenyl transfer agent, reduce the temperature of the polymerization reaction, reduce the solids content in the polymerization reaction mass (i.e., increase the solids content) or reduce the residence time of the polymerization.

Monomers

Monomers useful herein include olefins having from 2 to 40 carbon atoms, alternately 2 to 12 carbon atoms (preferably ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, and dodecene) and, optionally, also polyenes (such as dienes). Particularly preferred monomers include ethylene, and mixtures of C₂ to C₁₀ alpha olefins, such as ethylene-propylene, ethylene-hexene, ethylene-octene, propylene-hexene, and the like.

The catalyst systems described herein are also particularly effective for the polymerization of ethylene, either alone or in combination with at least one other olefinically unsaturated monomer, such as a C₃ to C₂₀ α-olefin, and particularly a C₃ to C₁₂ α-olefin. Likewise, the present complexes are also particularly effective for the polymerization of propylene, either alone or in combination with at least one other olefinically unsaturated monomer, such as ethylene or a C₄ to C₂₀ α-olefin, and particularly a C₄ to C₂₀ α-olefin.

The catalyst systems described herein are also particularly effective for the polymerization of ethylene and propylene, either alone or in combination with at least one other olefinically unsaturated monomer, such as a C₄ to C₂₀ diene, and particularly a C₃ to C₁₂ diene.

Examples of preferred α-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, 4-methylpentene-1, 3-methylpentene-1, 3, 5, 5-trimethylhexene-1, and 5-ethylnonene-1.

In some embodiments, the monomer mixture comprises one or more dienes at up to 10 wt %, such as from 0.00001 to 1.0 wt %, for example from 0.002 to 0.5 wt %, such as from 0.003 to 0.2 wt %, based upon the monomer mixture. Non-limiting examples of useful dienes include, cyclopentadiene, norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene, 1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, and 9-methyl-1,9-decadiene.

Where olefins are used that give rise to short chain branching, such as propylene, the catalyst systems may, under appropriate conditions, generate stereoregular polymers or polymers having stereoregular sequences in the polymer chains.

In a preferred embodiment, the catalyst systems described herein are used in any polymerization process described above to produce ethylene homopolymers or copolymers, propylene homopolymers or copolymers, particularly ethylene-propylene copolymers and copolymers and ethylene-propylene-diene monomer copolymers.

Scavengers

In some embodiments, when using the complexes described herein, particularly when they are immobilized on a support, the catalyst system will additionally comprise one or more scavenging compounds. Here, the term scavenging compound means a compound that removes polar impurities from the reaction environment. These impurities adversely affect catalyst activity and stability. Typically, the scavenging compound will be an organometallic compound such as the Group-13 organometallic compounds of U.S. Pat. Nos. 5,153,157; 5,241,025; WO 1991/09882; WO 1994/03506; WO 1993/14132; and that of WO 1995/07941. Exemplary compounds include triethyl aluminum, triethyl borane, tri-iso-butyl aluminum, methyl alumoxane, iso-butyl alumoxane, tri-n-octyl aluminum, bis(diisobutylaluminum)oxide, modified methylalumoxane. (Useful modified methylalumoxane include cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A) and those described in U.S. Pat. No. 5,041,584). Those scavenging compounds having bulky or C₆-C₂₀ linear hydrocarbyl substituents connected to the metal or metalloid center usually minimize adverse interaction with the active catalyst. Examples include triethylaluminum, but more preferably, bulky compounds such as tri-iso-butyl aluminum, tri-iso-prenyl aluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum. When alumoxane is used as the activator, any excess over that needed for activation will scavenge impurities and additional scavenging compounds may be unnecessary. Alumoxanes also may be added in scavenging quantities with other activators, e.g., methylalumoxane, [Me₂HNPh]⁺[B(pfp)₄]- or B(pfp)₃ (perfluorophenyl=pfp=C₆F₅).

In embodiments, the transfer agent, such as the aluminum vinyl transfer agent, may also function as a scavenger.

In a preferred embodiment, two or more catalyst complexes as described herein are combined with a chain transfer agent, such tri-n-octylaluminum, in the same reactor with monomer. Alternately, one or more complexes are combined with another catalyst (such as a metallocene) and a chain transfer agent, such as tri-n-octylaluminum, in the same reactor with monomer.

Polymer Products

While the molecular weight of the polymers produced herein is influenced by reactor conditions including temperature, monomer concentration and pressure, the presence of chain terminating agents and the like, the homopolymer and copolymer products produced by the present process may have an Mw of about 1,000 to about 2,000,000 g/mol, alternately of about 30,000 to about 600,000 g/mol, or alternately of about 100,000 to about 500,000 g/mol, as determined by Gel Permeation Chromatography. Preferred polymers produced herein may be homopolymers or copolymers. In a preferred embodiment, the comonomer(s) are present at up to 50 mol %, preferably from 0.01 to 40 mol %, preferably 1 to 30 mol %, preferably from 5 to 20 mol %.

The polymers produced by the process of the invention can be used in a wide variety of products and end-use applications. The polymers produced can be homo- and copolymers of ethylene and propylene and include linear low density polyethylene, elastomers, plastomers, high-density polyethylenes, medium density polyethylenes, low density polyethylenes, polypropylene and polypropylene copolymers. Polymers, typically ethylene based copolymers, have a density of from 0.86 g/cc to 0.97 g/cc; density being measured in accordance with ASTM-D-1238. Propylene based polymers produced include isotactic polypropylene, atactic polypropylene and random, or impact copolymers.

The polymers of embodiments of the invention may have an M_(n) (number-average molecular weight) value from 300 to 1,000,000, or between from 700 to 300,000 g/mol. For low weight molecular weight applications, such as those copolymers useful in lubricating and fuel oil compositions, an M_(n) of 300 to 20,000 is contemplated, or less than or equal to 10,000 g/mol. Additionally, copolymer of embodiments of the invention will comprise a molecular weight distribution (M_(w)/M_(n)) in the range of >1, or >1.5 or <6, or <4 or <3, preferably from greater than 1 to 40, alternatively from 1.5 to 20, alternatively from 1.5 to 10, alternatively from 1.6 to 6, alternatively from 1.5 to 4, or alternatively from 2 to 3.

Preferred propylene polymer, preferably homopolymer, produced herein has an M_(w) of 20,000 up to 2,000,000 g/mol.

For higher molecular weight applications, preferred polymer, preferably homopolymer, produced herein has an M_(w) of 20,000 up to 2,000,000 g/mol, alternately 50,000 to 1,500,000 g/mol, alternately 100,000 to 1,300,000 g/mol, alternately 300,000 to 1,300,000 g/mol, alternately 500,000 to 1,300,000 g/mol.

For higher molecular weight applications, preferred polymer, preferably homopolymer, produced herein has an M_(w) of 20,000 up to 2,000,000 g/mol and a g′vis of more than 0.5, alternately 0.90 or more, alternately 0.95 or more, alternately 0.98 or more.

For lower molecular weight applications, preferred polymer, preferably homopolymer, produced herein has an M_(w) of less than 100,000 g/mol and a g′vis of 0.90 or less, alternately 0.85 or less, alternately 0.80 or less, alternately 0.75 or less, alternately 0.70 or less, alternately 0.60 or less.

End Uses

The polymers of this invention may be blended and/or coextruded with any other polymer. Non-limiting examples of other polymers include linear low density polyethylenes, elastomers, plastomers, high pressure low density polyethylene, high density polyethylenes, isotactic polypropylene, ethylene propylene copolymers and the like.

Articles made using polymers produced herein may include, for example, molded articles (such as containers and bottles, e.g., household containers, industrial chemical containers, personal care bottles, medical containers, fuel tanks, and storageware, toys, sheets, pipes, tubing) films, non-wovens, and the like. It should be appreciated that the list of applications above is merely exemplary, and is not intended to be limiting.

In particular, polymers produced by the process of the invention and blends thereof are useful in such forming operations as film, sheet, and fiber extrusion and coextrusion as well as blow molding, injection molding, roto-molding. Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing film or oriented films.

EXPERIMENTAL

All manipulations were performed under an inert atmosphere using glove box techniques unless otherwise stated. Benzene-d₆ (Cambridge Isotopes or Sigma Aldrich) was degassed and dried over 3A molecular sieves prior to use. CDCl₃ (Deutero GmbH) was used as received.

Diisobutylaluminum hydride (DIBAL-H) was purchased from Akzo Nobel Surface Chemistry LLC and used as received. Triisobutyl aluminum (TIBAL) was purchased from Akzo Nobel and was used as received. 1,7-octadiene were purchased from Sigma Aldrich and purified by the following procedure prior to use. The diene was purged under nitrogen for 30 minutes and then this was stored over 3A molecular sieves for overnight. Further this was stirred with NaK (sodium-potassium alloy) for overnight and then filtered through basic alumina column prior to use. 1,9-decadiene was purified by prior to use.

Preparation of Isobutyldi(oct-7-en-1-yl)aluminum, ^(i)BuAl(Oct=)₂ (AVTA1)

A neat 1,7-octadiene (34.85 g, 316 mmol) was added to DIBAL-H (3.980 g, 28.0 mmol) at room temperature. The resulting mixture was stirred under reflux at 110° C. for 60 minutes and then continuously stirred at 70° C. overnight. The excess 1,7-octadiene from the reaction mixture was removed in vacuo to obtain a colorless viscous oil of AVTA1 (8.10 g, 97%). The product formation was confirmed by ¹H NMR and based on the relative integration the molecular formula of was assigned as (C₄H₉)_(1.17)Al(CsH₁₅)_(1.83). ¹H NMR (400 MHz, benzene-d₆): δ=5.81 (m, 2H, ═CH), 5.05 (m, 4H, ═CH₂), 2.03 (m, 8H, —CH₂), 1.59 (m, 1H, iBu-CH), 1.38 (m, 12H, —CH₂), 1.09 (d, 6H, iBu-CH₃), 0.51 (t, 4H, Al—CH₂), 0.31 (d, 2H, iBu-CH₂) ppm.

Preparation of Isobutyldi(oct-7-en-1-yl)aluminum, ^(i)BuAl(Oct=)₂ (AVTA2)

1,7-Octadiene (250 mL, 1.69 mol) was loaded into a round-bottomed flask. Diisobutylaluminum hydride (27.4 mL, 0.153 mol) was added dropwise over 20 minutes. The mixture was then placed into a metal block maintained at 117° C. After about 20 minutes the solution reached 107° C. and maintained this temperature. Gas evolution was observed at this time. After 125 minutes the mixture was cooled to ambient temperature and the volatiles were removed to afford a nearly colorless oil. The oil was placed under reduced pressure (ca. 60 mTorr) and warmed to 50° C. for 30 minutes to remove any trace 1,7-octadiene. H-NMR spectroscopic data indicated that the product had the average formula of Al(i-Bu)_(0.86)(octenyl)_(2.14) with an additional 0.2 molar equivalent of what is presumed to be the triene formed by the insertion of 1,7-octadiene into an Al-octenyl bond followed by beta hydride elimination. Yield: 54.0 g.

Preparation of Isobutyldi(dec-9-en-1-yl)aluminum, ^(i)BuAl(Dec=)₂ (AVTA3)

1,9-Decadiene (500 mL, 2.71 mol) was loaded into a round bottomed flask. Diisobutylaluminum hydride (30.2 mL, 0.170 mol) was added dropwise over 15 minutes. The mixture was then placed in a metal block maintained at 110° C. After 30 minutes the solution had stabilized at a temperature of 104+C. The mixture was kept at this temperature for an additional 135 minutes at which time H-NMR spectroscopic data indicated that the reaction had progressed to the desired amount. Cooled to ambient temperature. The excess 1,9-decadiene was removed by vacuum distillation at 44° C./120 mTorr over a 2.5 hours. The product was further distilled at 50° C./120 mTorr for an additional hour to ensure complete removal of all 1,9-decadiene. The isolated product was a clear colorless oil. HNMR spectroscopic data suggests an average formulation of Al(i-Bu)_(0.9)(decenyl)_(2.1) with an additional ca. 0.2 molar equivalent of what is presumed to be the triene formed by the insertion of 1,9-decadiene into an Al-decenyl bond followed by beta hydride elimination. Yield: 70.9 g.

Catalyst Complexes

Complex A was prepared as described in 62/357,033, filed Jun. 30, 2016. Complex B was prepared as follows:

8-(2,6-Diisopropylphenylamino)quinolin-2(1H)-one

To a suspension of NaH (5.63 g of 60 wt % in mineral oil, 140 mmol) in tetrahydrofuran (1000 mL) was added 8-bromoquinolin-2(1H)-one (30.0 g, 134 mmol) in small portions at 0° C. The obtained reaction mixture was warmed to room temperature, stirred for 30 min, and then cooled to 0° C. Then t-butyldimethylsilylchloride (20.2 g, 134 mmol) was added in one portion. This mixture was stirred for 30 min at room temperature and then poured into water (1 L). The protected 8-bromoquinolin-2(1H)-one was extracted with diethyl ether (3×400 mL). The combined extracts were dried over Na₂SO₄ and then evaporated to dryness. Yield 45.2 g (quant., 99% purity by GC/MS) of a dark red oil. To a solution of 2,6-diisopropylaniline (27.7 mL, 147 mmol) and toluene (1.5 L) was added n-butyllithium (60.5 mL, 147 mmol, 2.5 M in hexanes) at room temperature. The obtained suspension was heated briefly to 100° C. and then cooled to room temperature. To the reaction mixture was added Pd₂(dba)₃ (dba=dibenzylideneacetone) (2.45 g, 2.68 mmol) and XPhos (XPhos=2-Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl) (2.55 g, 5.36 mmol) followed by the addition of the protected 8-bromoquinolin-2(1H)-one (45.2 g, 134 mmol). The obtained dark brown suspension was heated at 60° C. until lithium salt precipitate disappeared (ca. 30 min). The resulting dark red solution was quenched by addition of water (100 mL), and the organic layer was separated, dried over Na₂SO₄ and then evaporated to dryness. The obtained oil was dissolved in a mixture of dichloromethane (1000 mL) and methanol (500 mL), followed by an addition of 12 M HCl (50 mL). The reaction mixture was stirred at room temperature for 3 h, then poured into 5% K₂CO₃ (2 L). The product was extracted with dichloromethane (3×700 mL). The combined extracts were dried over Na₂SO₄, filtered, and then evaporated to dryness. The resulting solid was triturated with n-hexane (300 mL), and the obtained suspension collected on a glass frit. The precipitate was dried in vacuum. Yield 29.0 g (67%) of a marsh-green solid. Anal. calc. for C₂₁H₂₄N₂O: C, 78.71; H, 7.55; N, 8.74. Found: C, 79.00; H, 7.78; N, 8.50. ¹H NMR (CDCl₃): δ 13.29 (br.s, 1H), 7.80-7.81 (d, 1H, J=9.5 Hz), 7.35-7.38 (m, 1H), 7.29-7.30 (m, 3H), 6.91-6.95 (m, 2H), 6.58-6.60 (d, 1H, J=9.5 Hz), 6.27-6.29 (m, 1H), 3.21 (sept, 2H, J=6.9 Hz), 1.25-1.26 (d, 6H, J=6.9 Hz), 1.11-1.12 (d, 6H, J=6.9 Hz).

2-Chloro-N-(2,6-diisopropylphenyl)quinolin-8-amine

29.0 g (90.6 mmol) of 8-(2,6-diisopropylphenylamino)quinolin-2(1H)-one was added to 400 mL of POCl₃ in one portion. The resulting suspension was heated for 40 h at 105° C., then cooled to room temperature, and poured into 4000 cm³ of a crushed ice. The crude product was extracted with 3×400 mL of diethyl ether. The combined extract was dried over K₂CO₃ and then evaporated to dryness. The resulting solid was triturated with 30 mL of cold n-hexane, and the formed suspension was collected on a glass frit. The obtained solid was dried in vacuum. Yield 29.0 g (95%) of a yellow-green solid. Anal. calc. for C₂₁H₂₃N₂Cl: C, 74.43; H, 6.84; N, 8.27. Found: C, 74.68; H, 7.02; N, 7.99. ¹H NMR (CDCl₃): δ 8.04-8.05 (d, 1H, J=8.6 Hz), 7.38-7.39 (d, 1H, J=8.5 Hz), 7.33-7.36 (m, 1H), 7.22-7.27 (m, 4H), 7.04-7.06 (d, 1H, J=8.1 Hz), 6.27-6.29 (d, 1H, J=7.8 Hz), 3.20 (sept, 2H, J=6.9 Hz), 1.19-1.20 (d, 6H, J=6.9 Hz), 1.10-1.11 (d, 6H, J=6.9 Hz).

8-Bromo-1,2,3,4-tetrahydronaphthalen-1-ol

To a mixture of 78.5 g (530 mmol) of 1,2,3,4-tetrahydronaphthalen-1-ol, 160 mL (1.06 mol) of TMEDA, and 3000 mL of pentane cooled to −20° C. 435 mL (1.09 mol) of 2.5 M ^(n)BuLi in hexanes was added dropwise. The obtained mixture was refluxed for 12 h, then cooled to −80° C., and 160 mL (1.33 mol) of 1,2-dibromotetrafluoroethane was added. The obtained mixture was allowed to warm to room temperature and then stirred for 12 h at this temperature. After that, 100 mL of water was added. The resulting mixture was diluted with 2000 mL of water, and the organic layer was separated. The aqueous layer was extracted with 3×400 mL of toluene. The combined organic extract was dried over Na₂SO₄ and then evaporated to dryness. The residue was distilled using the Kugelrohr apparatus, b.p. 150-160° C./1 mbar. The obtained yellow oil was dissolved in 100 mL of triethylamine, and the formed solution was added dropwise to a stirred solution of 71.0 mL (750 mmol) of acetic anhydride and 3.00 g (25.0 mmol) of DMAP in 105 mL of triethylamine. The formed mixture was stirred for 5 min, then 1000 mL of water was added, and the obtained mixture was stirred for 12 h. After that, the reaction mixture was extracted with 3×200 mL of ethyl acetate. The combined organic extract was washed with aqueous Na₂CO₃, dried over Na₂SO₄, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=30:1, vol.). The isolated ester was dissolved in 1500 mL of methanol, 81.0 g (1.45 mol) of KOH was added, and the obtained mixture was heated to reflux for 3 h. The reaction mixture was then cooled to room temperature and poured into 4000 mL of water. The title product was extracted with 3×300 mL of dichloromethane. The combined organic extract was dried over Na₂SO₄ and then evaporated to dryness. Yield 56.0 g (47%) of a white crystalline solid. ¹H NMR (CDCl₃): δ 7.38-7.41 (m, 1H, 7-H); 7.03-7.10 (m, 2H, 5,6-H); 5.00 (m, 1H, 1-H), 2.81-2.87 (m, 1H, 4/4′-H), 2.70-2.74 (m, 1H, 4′/4-H), 2.56 (br.s., 1H, OH), 2.17-2.21 (m, 2H, 2,2′-H), 1.74-1.79 (m, 2H, 3,3′-H).

8-Bromo-3,4-dihydronaphthalen-1(2H)-one

To a solution of 56.0 g (250 mmol) of 8-bromo-1,2,3,4-tetrahydronaphthalen-1-ol in 3500 mL of dichloromethane was added 265 g (1.23 mol) of pyridinium chlorochromate (PCC). The resulting mixture was stirred for 5 h at room temperature, then passed through a pad of silica gel 60 (500 mL; 40-63 um), and finally evaporated to dryness. Yield 47.6 g (88%) of a colorless solid. ¹H NMR (CDCl₃): δ 7.53 (m, 1H, 7-H); 7.18-7.22 (m, 2H, 5,6-H); 2.95 (t, J=6.1 Hz, 2H, 4,4′-H); 2.67 (t, J=6.6 Hz, 2H, 2,2′-H); 2.08 (quint, J=6.1 Hz, J=6.6 Hz, 2H, 3,3′-H).

(8-Bromo-1,2,3,4-tetrahydronaphthalen-1-yl)phenylamine

To a stirred solution of 21.6 g (232 mmol) of aniline in 140 mL of toluene was added 10.93 g (57.6 mmol) of TiCl₄ over 30 min at room temperature under argon atmosphere. The resulting mixture was stirred for 30 min at 90° C. followed by an addition of 13.1 g (57.6 mmol) of 8-bromo-3,4-dihydronaphthalen-1(2H)-one. This mixture was stirred for 10 min at 90° C., then cooled to room temperature, and poured into 500 mL of water. The product was extracted with 3×50 mL of ethyl acetate. The combined organic extract was dried over Na₂SO₄, evaporated to dryness, and the residue was re-crystallized from 10 mL of ethyl acetate. The obtained crystalline solid was dissolved in 200 mL of methanol, 7.43 g (118 mmol) of NaBH₃CN and 3 mL of acetic acid were added in argon atmosphere. This mixture was heated to reflux for 3 h, then cooled to room temperature, and evaporated to dryness. The residue was diluted with 200 mL of water, and crude product was extracted with 3×100 mL of ethyl acetate. The combined organic extract was dried over Na₂SO₄ and evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate-triethylamine=100:10:1, vol.). Yield 13.0 g (75%) of a yellow oil. Anal. Calc. for Cl₆H₁₆BrN: C, 63.59; H, 5.34; N, 4.63. Found: C, 63.82; H, 5.59; N, 4.49. ¹H NMR (CDCl₃): δ 7.44 (m, 1H), 7.21 (m, 2H), 7.05-7.11 (m, 2H), 6.68-6.73 (m, 3H), 4.74 (m, 1H), 3.68 (br.s, 1H, NH), 2.84-2.89 (m, 1H), 2.70-2.79 (m, 1H), 2.28-2.32 (m, 1H), 1.85-1.96 (m, 1H), 1.76-1.80 (m, 1H), 1.58-1.66 (m, 1H).

N-Phenyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydronaphthalen-1-amine

To a solution of 13.0 g (43.2 mmol) of (8-bromo-1,2,3,4-tetrahydronaphthalen-1-yl)phenylamine in 250 mL THF was added 17.2 mL (43.0 mmol) of 2.5 M ^(n)BuLi at −80° C. Further on, this mixture was stirred for 1 h at this temperature, and 56.0 mL (90.3 mmol) of 1.6 M ^(t)BuLi in pentane was added. The resulting mixture was stirred for 1 h at the same temperature. Then, 16.7 g (90.0 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. After that the cooling bath was removed, and the resulting mixture was stirred for 1 h at room temperature. Finally, 10 mL of water was added, and the obtained mixture was evaporated to dryness. The residue was diluted with 200 mL of water, and crude product was extracted with 3×100 mL of ethyl acetate. The combined organic extract was dried over Na₂SO₄ and then evaporated to dryness. Yield 15.0 g (98%) of a yellow oil. Anal. Calc. for C₂₂H₂₈BNO₂: C, 75.65; H, 8.08; N, 4.01. Found: C, 75.99; H, 8.32; N, 3.79. ¹H NMR (CDCl₃): δ 7.59 (m, 1H), 7.18-7.23 (m, 4H), 6.71-6.74 (m, 3H), 5.25 (m, 1H), 3.87 (br.s, 1H, NH), 2.76-2.90 (m, 2H), 2.12-2.16 (m, 1H), 1.75-1.92 (m, 3H), 1.16 (s, 6H), 1.10 (s, 6H).

2-(8-Anilino-5,6,7,8-tetrahydronaphthalen-1-yl)-N-(2,6-diisopropylphenyl)quinolin-8-amine (QDA-1)

To a solution of 13.8 g (41.0 mmol) of 2-chloro-N-(2,6-diisopropylphenyl)quinolin-8-amine in 700 mL of 1,4-dioxane were added 15.0 g (43.0 mmol) of N-phenyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydronaphthalen-1-amine, 35.0 g (107 mmol) of cesium carbonate and 400 mL of water. The obtained mixture was purged with argon for 10 min followed by an addition of 2.48 g (2.15 mmol) of Pd(PPh₃)₄. The formed mixture was stirred for 2 h at 90° C., then cooled to room temperature. To the obtained two-phase mixture 700 mL of n-hexane was added. The organic layer was separated, washed with brine, dried over Na₂SO₄, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate-triethylamine=100:5:1, vol.) and then re-crystallized from 150 mL of n-hexane. Yield 15.1 g (70%) of a yellow powder. Anal. calc. for C₃₇H₃₉N₃: C, 84.53; H, 7.48; N, 7.99. Found: C, 84.60; H, 7.56; N, 7.84. ¹H NMR (CDCl₃): δ 7.85-7.87 (d, J=7.98 Hz, 1H), 7.56 (br.s, 1H), 7.43-7.45 (d, J=8.43 Hz, 1H), 7.21-7.38 (m, 6H), 7.12 (t, J=7.77 Hz, 1H), 6.87-6.89 (d, J=7.99 Hz, 1H), 6.74 (t, J=7.99 Hz, 1H), 6.36 (t, J=7.32 Hz, 1H), 6.14-6.21 (m, 3H), 5.35 (br.s, 1H), 3.56 (br.s, 1H), 3.20-3.41 (m, 2H), 2.83-2.99 (m, 2H), 2.10-2.13 (m, 1H), 1.77-1.92 (m, 3H), 1.13-1.32 (m, 12H).

Complex B: (QDA-1)HfMe₂

Benzene (50 mL) was added to QDA-1 (2.21 g, 4.20 mmol) and Hf(NMe₂)₄(1.58 g, 4.45 mmol) to form a clear orange solution. The mixture was heated to reflux for 16 hours to form a clear red-orange solution. Most of the volatiles were removed by evaporation under a stream of nitrogen to afford a concentrated red solution (ca. 5 mL) that was warmed to 40° C. Then hexane (30 mL) was added and the mixture was stirred to cause orange crystalline solid to form. This slurry was cooled to −40° C. for 30 minutes then the solid was collected by filtration and washed with additional cold hexane (2×10 mL). The resulting orange solid of (QDA-1)Hf(NMe₂)₂ was dried under reduced pressure (2.90 g, 3.67 mmol, 87.4% yield). This solid was dissolved in toluene (25 mL) and Me₃A1 (12.8 mL, 25.6 mmol) was added. The mixture was warmed to 40° C. for 1 hour then evaporated under a stream of nitrogen. The crude product (2.54 g) was ˜90% pure by HNMR spectroscopy. The solid was purified by recrystallization from CH₂Cl₂-hexanes (20 mL-20 mL) by slow evaporation to give pure product as orange crystals (1.33 g, 43.2% from ligand). The mother liquor was further concentrated for a second crop (0.291 g, 9.5% from ligand).

Polymerization Examples

Solutions of the pre-catalysts (complexes A and B) were made using toluene (ExxonMobil Chemical—anhydrous, stored under N2) (98%). Pre-catalyst solutions were typically 0.5 mmol/L.

Solvents, polymerization grade toluene and/or isohexanes were supplied by ExxonMobil Chemical Co. and are purified by passing through a series of columns: two 500 cc Oxyclear cylinders in series from Labclear (Oakland, Calif.), followed by two 500 cc columns in series packed with dried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cc columns in series packed with dried 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company).

1-octene (C8; 98%, Aldrich Chemical Company) was dried by stirring over NaK overnight followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1).

Polymerization grade ethylene (C2) was used and further purified by passing it through a series of columns: 500 cc Oxyclear cylinder from Labclear (Oakland, Calif.) followed by a 500 cc column packed with dried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), and a 500 cc column packed with dried 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company).

Polymerization grade propylene (C3) was used and further purified by passing it through a series of columns: 2250 cc Oxiclear cylinder from Labclear followed by a 2250 cc column packed with 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), then two 500 cc columns in series packed with 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company), then a 500 cc column packed with Selexsorb CD (BASF), and finally a 500 cc column packed with Selexsorb COS (BASF).

For polymerization runs collected in Tables 1, 4, and 6, bis(diisobutylaluminum)oxide (DiBAl-O, AkzoNobel 0.92M in hexane) was used as a scavenger prior to introduction of the AVTA, activator and pre-catalyst into the reactor. Scavenger was typically used as a 5 mmol/L solution in toluene.

Tri-n-octyl aluminum (TnOAl, neat, AkzoNobel) was used as a comparative to the AVTA's and was typically used as a 5 or 10 mmol/L solution in toluene. The AVTA's were typically also used as a 5 or 10 mmol/L solution in toluene. AVTA# in Tables 1, 4, and 6, correspons to the AVTA's prepared in the examples above.

Reactor Description and Preparation:

Polymerizations were conducted in an inert atmosphere (N₂) drybox using autoclaves equipped with an external heater for temperature control, glass inserts (internal volume of reactor=23.5 mL for C2 and C2/C8; 22.5 mL for C3 and C2/C3 runs), septum inlets, regulated supply of nitrogen, ethylene and propylene, and equipped with disposable PEEK mechanical stirrers (800 RPM). The autoclaves were prepared by purging with dry nitrogen at 110° C. or 115° C. for 5 hours and then at 25° C. for 5 hours.

Ethylene Polymerization (PE) or Ethylene/1-octene Copolymerization (EO):

The reactor was prepared as described above, and then purged with ethylene. Isohexanes, 1-octene (50 μL for EO runs), and DiBAl-O scavenger (0.05 umol) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (values indicated below) and charged with ethylene to process pressure (100 psig=790.8 kPa) while stirring at 800 RPM. The AVTA solution was injected via syringe to the reactor at process conditions. Next, the activator solution, followed by the pre-catalyst solution, was injected via syringe to the reactor at process conditions. Ethylene was allowed to enter (through the use of computer controlled solenoid valves) the autoclaves during polymerization to maintain reactor gauge pressure (+/−2 psig). Reactor temperature was monitored and typically maintained within +/−1° C. Polymerizations were halted by addition of approximately 50 psi O₂/Ar (5 mole % O₂) gas mixture to the autoclave for approximately 30 seconds. The polymerizations were quenched after a predetermined cumulative amount of ethylene had been added (maximum quench value in psid) or for a maximum of 30 minutes polymerization time. Afterwards, the reactors were cooled and vented. Polymers were isolated after the solvent was removed in-vacuo. Yields reported include total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol transition metal compound per hour of reaction time (g/mmol*hr). Ethylene homopolymerization runs and ethylene/1-octene copolymerization runs are summarized in Table 6.

Ethylene-Propylene Copolymerization (EP):

The reactor was prepared as described above, then heated to 40° C., and then purged with ethylene gas at atmospheric pressure. Ethylene was then added at 125 psid (790.8 kPa) to the reactor. Isohexanes and scavenger (DiBAl-O, 0.5 μmol) were added via syringe. The stirrers were then started and maintained at 800 RPM. Liquid propylene (0.5 ml) was then injected into the reactor. The reactor was then brought to process temperature (85° C. or 100° C.). The AVTA or control TnOAl solutions were next injected into the reactor at process temperature. Next, the activator solution, followed by the pre-catalyst solution, was injected via syringe to the reactor at process conditions. Reactor temperature was monitored and typically maintained within +/−1° C. Polymerizations were halted by addition of approximately 50 psi O2/Ar (5 mole % O2) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched based on a predetermined pressure loss (quench value) of approximately 4 psid pressure loss or for a maximum of 30 minutes polymerization time. The reactors were cooled and vented. The polymer was isolated after the solvent was removed in-vacuo. The quench times are reported in Table 1 for each run. Yields reported include total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol transition metal compound per hour of reaction time (g/mmol*hr). Ethylene/propylene copolymerization examples are collected in Table 1 and additional information is located above the table.

Propylene Homopolymerization (PP):

The reactor was prepared as described above, then heated to 40° C., and then purged with propylene gas at atmospheric pressure. Isohexanes, propylene (1.0 ml) and scavenger (DiBAl-O, 0.5 μmol) were added via syringe. The reactor was then brought to process temperature (85° C. or 100° C.) while stirring at 800 RPM. The AVTA or control TnOAl solutions were next injected into the reactor at process temperature. The activator solution, followed by the pre-catalyst solution, were injected via syringe to the reactor at process conditions. Reactor temperature was monitored and typically maintained within +/−1° C. Polymerizations were halted by addition of approximately 50 psi O₂/Ar (5 mole % O₂) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched based on a predetermined pressure loss of approximately 8 psid (max quench value in psi) loss, or for a maximum of 30 minutes polymerization time. The reactors were cooled and vented. The polymers were isolated after the solvent was removed in-vacuo. The actual quench times are reported in Table 4 for each run. Yields reported include total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol transition metal compound per hour of reaction time (g/mmol*hr). Propylene homopolymerization examples are reported in Table 4 and additional information is located above the table.

Polymer Characterization

For analytical testing, polymer sample solutions were prepared by dissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity from Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99% from Aldrich) at 165° C. in a shaker oven for approximately 3 hours. The typical concentration of polymer in solution was between 0.1 to 0.9 mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB. Samples were cooled to 135° C. for testing.

High temperature size exclusion chromatography was performed using an automated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated herein by reference. Molecular weights (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD=Mw/Mn), which is also sometimes referred to as the polydispersity (PDI) of the polymer, were measured by Gel Permeation Chromatography using a Symyx Technology GPC equipped with dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw) between 580 and 3,039,000). Samples (250 μL of a polymer solution in TCB were injected into the system) were run at an eluent flow rate of 2.0 mL/minute (135° C. sample temperatures, 165° C. oven/columns) using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series. No column spreading corrections were employed. Numerical analyses were performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. The molecular weights obtained are relative to linear polystyrene standards. Molecular weight data is reported in Tables 1, 4 and 6 under the headings Mn, Mw and PDI (or Mw/Mn) as defined above.

Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymers. Samples were pre-annealed at 220° C. for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C./minute and then cooled at a rate of 50° C./minute. Melting points were collected during the heating period for the second melt. The results are reported in the Tables 1, 4 and 6 under the heading, Tm (° C.).

Samples for infrared analysis were prepared by depositing the stabilized polymer solution onto a silanized wafer (Part number S10860, Symyx). By this method, approximately between 0.12 and 0.24 mg of polymer is deposited on the wafer cell. The samples were subsequently analyzed on a Brucker Equinox 55 FTIR spectrometer equipped with Pikes' MappIR specular reflectance sample accessory. Spectra, covering a spectral range of 5000 cm⁻¹ to 500 cm⁻¹, were collected at a 2 cm⁻¹ resolution with 32 scans.

For ethylene-1-octene copolymers, the wt % octene in the copolymer was determined via measurement of the methyl deformation band at −1375 cm⁻¹. The peak height of this band was normalized by the combination and overtone band at −4321 cm⁻¹, which corrects for path length differences. The normalized peak height was correlated to individual calibration curves from ¹H NMR data to predict the wt % octene content within a concentration range of −2 to 35 wt % for octene. Typically, R² correlations of 0.98 or greater are achieved. (These numbers are reported in Table 6 under the heading C8 wt %.)

Unless otherwise indicated, proton NMR spectra are collected using a 400 MHz Varian pulsed fourier transform NMR spectrometer equipped with a variable temperature proton detection probe operating at 120° C. The polymer sample is dissolved in 1,1,2,2-tetrachloroethane-d2 (TCE-d2) and transferred into a 5 mm glass NMR tube. Typical acquisition parameters are sweep width=10 KHz, pulse width=30 degrees, acquisition time=2 s, acquisition delay=5 s and number of scans=120. Chemical shifts are determined relative to the TCE-d2 signal which is set to 5.98 ppm.

The chain end unsaturations are determined as follows. The vinyl resonances of interest are between from about 5.0 to 5.1 ppm (VRA), the vinylidene resonances between from about 4.65 to 4.85 ppm (VDRA), the vinylene resonances from about 5.31 to 5.55 ppm (VYRA), the tri-substituted unsaturated species from about 5.11 to 5.30 ppm (TSRA) and the aliphatic region of interest between from about 0 to 2.1 ppm (IA). The number of vinyl groups/1000 Carbons is determined from the formula: (VRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA). Likewise, the number of vinylidene groups/1000 Carbons is determined from the formula: (VDRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA), the number of vinylene groups/1000 Carbons from the formula (VYRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA) and the number of tri-substituted groups from the formula (TSRA*1000)/((IA+VRA+VYRA+VDRA)/2)+TSRA). VRA, VDRA, VYRA, TSRA and IA are the integrated normalized signal intensities in the chemical shift regions defined above. Proton NMR data is reported in Tables 2 and 5. For many examples, end-group unsaturation was below the detection limit, or noise level, and could not be determined.

GPC3D data is reported in Table 3 and is described further below.

For the polymerization results collected in the Tables below, “Ex#” stands for example number. Under the Ex# column heading, the following abbreviations are defined: PE=polyethylene, EO=ethylene-1-octene copolymer, PP=polypropylene and EP=ethylene-propylene copolymer, TMC identifies the pre-catalyst/complex used, T (° C.) is the polymerization temperature which was typically maintained within +/−1° C. “Yield” is polymer yield, and is not corrected for catalyst residue. “Quench time (s)” is the actual duration of the polymerization run in seconds. “Quench Value (psid)” for ethylene based polymerization runs (no propylene) is the set maximum amount of ethylene uptake (conversion) for the experiment. If a polymerization quench time is less than the maximum time set, then the polymerization ran until the set maximum value of ethylene uptake was reached. For ethylene-propylene copolymerization runs, quench value indicates the maximum set pressure loss (conversion) of ethylene and propylene combined during the polymerization. For propylene homopolymerization runs, quench value indicates the maximum set pressure loss (conversion) of propylene during the polymerization. Activity is reported at grams polymer per mmol of catalyst per hour.

TABLE 1 High throughput ethylene-propylene (EP) runs using tri-n-octyl aluminum (TNOAl) or AVTA1. Conditions: For all examples in Table 1, 0.025 μmol of complex A was used as the pre-catalyst and activated with 1.1 molar equivalents of dimethylanilinium tetrakis(pentafluorophenyl)borane. Propylene (0.5 ml) was added, and the total reagent and solvent volume in the reactor was 5 ml. All runs utilized 0.05 μmol of bis(diisobutyl aluminum)oxide as scavenger. Ethylene (125 psid) was added before catalyst injection and no further ethylene was added to the reactor. The run was quenched after 4 psid (Quench Value) of reactor pressure loss. Maximum quench time was set to 30 minutes. AVTA AVTA or Iso- Activity (g PDI or TnOAl hexane Toluene T quench yield P/mmol Mn Mw Mz (Mw/ Tm Ex# TnOAl (umol) (uL) (uL) (° C.) time (s) (g) cat · hr) (g/mol) (g/mol) (g/mol) Mn) (° C.) EP-1 TNOAL 0.251 4103 272 85 23 0.1493 934,748 292,208 535,733 1,054,060 1.83 46.6 EP-2 TNOAL 1.001 3952 422 85 6 0.1445 3,468,000 117,860 176,507 308,465 1.50 44.4 EP-3 TNOAL 2.001 3752 622 85 3 0.1558 7,478,400 68,276 100,143 170,786 1.47 44.6 EP-4 TNOAL 0.251 4103 272 100 25 0.1323 762,048 276,616 449,079 850,755 1.62 46.6 EP-5 TNOAL 1.001 3952 422 100 4 0.1253 4,510,800 94,215 146,449 267,283 1.55 46.3 EP-6 TNOAL 2.001 3752 622 100 3 0.1278 6,134,400 60,138 87,166 159,408 1.45 44.5 EP-7 TNOAL 2.501 3903 471 85 3 0.1568 7,526,400 54,180 77,479 130,584 1.43 42.9 EP-8 TNOAL 3.501 3802 571 85 3 0.1557 7,473,600 43,016 61,457 102,806 1.43 43.5 EP-9 TNOAL 4.001 3752 621 85 3 0.1486 7,132,800 36,797 51,760 85,448 1.41 44.0 EP-10 TNOAL 2.501 3903 471 100 3 0.1344 6,451,200 46,290 66,224 109,631 1.43 44.0 EP-11 TNOAL 3.501 3802 571 100 2 0.1338 9,633,600 35,040 50,519 88,353 1.44 43.5 EP-12 TNOAL 4.001 3752 621 100 2 0.1288 9,273,600 32,889 46,253 79,734 1.41 44.7 EP-13 AVTA1 0.251 4103 272 85 25 0.1566 902,016 463,034 926,140 2,022,783 2.00 48.0 EP-14 AVTA1 0.501 4053 322 85 34 0.1596 675,953 420,892 699,328 1,265,888 1.66 48.5 EP-15 AVTA1 1.001 3953 422 85 29 0.1578 783,559 239,097 437,480 888,219 1.83 46.3 EP-16 AVTA1 0.251 4103 272 100 34 0.1258 532,800 341,323 703,230 1,518,486 2.06 47.5 EP-17 AVTA1 0.501 4053 322 100 38 0.1397 529,389 293,966 532,964 1,036,153 1.81 47.7 EP-18 AVTA1 1.001 3953 422 100 9 0.1197 1,915,200 202,179 352,395 714,063 1.74 49.4 EP-19 AVTA1 0.251 4103 272 85 27 0.1539 820,800 438,042 975,027 2,407,966 2.23 48.3 EP-20 AVTA1 0.501 4053 322 85 38 0.1575 596,842 434,287 797,340 1,957,466 1.84 48.9 EP-21 AVTA1 1.001 3953 422 85 39 0.1443 532,800 303,658 501,177 1,015,472 1.65 48.3 EP-22 AVTA1 0.251 4103 272 100 46 0.1309 409,774 365,325 767,535 1,716,813 2.10 47.5 EP-23 AVTA1 0.501 4053 322 100 34 0.1375 582,353 304,461 595,080 1,311,158 1.95 47.6 EP-24 AVTA1 1.001 3953 422 100 14 0.1259 1,294,971 237,702 409,097 925,670 1.72 46.3 EP-25 AVTA1 1.501 3852 522 85 13 0.1338 1,482,092 203,610 348,970 758,806 1.71 46.8 EP-26 AVTA1 2.001 3752 622 85 9 0.1216 1,945,600 170,457 286,096 610,025 1.68 45.2 EP-27 AVTA1 2.501 3902 472 85 7 0.1478 3,040,457 106,614 186,693 410,714 1.75 45.4 EP-28 AVTA1 1.501 3852 522 100 7 0.1112 2,287,543 157,969 278,726 573,185 1.76 46.3 EP-29 AVTA1 2.001 3752 622 100 6 0.1003 2,407,200 126,624 217,002 433,449 1.71 44.6 EP-30 AVTA1 2.501 3902 472 100 4 0.1271 4,575,600 93,687 153,141 314,987 1.63 44.7 EP-31 AVTA1 1.501 3852 522 85 5 0.0974 2,805,120 150,379 273,127 701,611 1.82 44.2 EP-32 AVTA1 2.001 3752 622 85 7 0.1189 2,445,943 153,765 274,790 614,577 1.79 44.0 EP-33 AVTA1 2.501 3902 472 85 6 0.1518 3,643,200 100,044 189,835 448,573 1.90 43.9 EP-34 AVTA1 1.501 3852 522 100 8 0.1092 1,965,600 159,136 282,274 617,642 1.77 47.1 EP-35 AVTA1 2.001 3752 622 100 6 0.0975 2,340,000 123,227 216,535 482,359 1.76 49.0 EP-36 AVTA1 2.501 3902 472 100 4 0.1238 4,456,800 87,342 155,183 356,179 1.78 45.1 EP-37 AVTA1 3.001 3853 521 85 7 0.1061 2,182,629 76,426 132,373 276,128 1.73 44.0 EP-38 AVTA1 3.501 3803 571 85 7 0.1029 2,116,800 75,629 128,342 273,071 1.70 44.4 EP-39 AVTA1 4.001 3752 621 85 6 0.0979 2,349,600 62,586 114,406 266,021 1.83 43.2 EP-40 AVTA1 3.001 3853 521 100 4 0.1166 4,197,600 69,880 121,293 265,051 1.74 46.1 EP-41 AVTA1 3.501 3803 571 100 3 0.1157 5,553,600 63,137 104,149 204,886 1.65 44.7 EP-42 AVTA1 4.001 3752 621 100 3 0.1225 5,880,000 57,723 97,341 200,023 1.69 43.7 EP-43 AVTA1 3.001 3853 521 85 7 0.1044 2,147,657 74,592 128,605 289,895 1.72 44.2 EP-44 AVTA1 3.501 3803 571 85 6 0.1083 2,599,200 77,638 123,454 255,841 1.59 42.9 EP-45 AVTA1 4.001 3752 621 85 7 0.1002 2,061,257 59,533 99,716 201,140 1.67 43.7 EP-46 AVTA1 3.001 3853 521 100 4 0.1020 3,672,000 63,582 114,103 262,787 1.79 44.9 EP-47 AVTA1 3.501 3803 571 100 4 0.1093 3,934,800 57,802 101,911 237,121 1.76 44.9 EP-48 AVTA1 4.001 3752 621 100 4 0.0950 3,420,000 54,987 90,747 202,879 1.65 44.6

TABLE 2 ¹H NMR data for select EP samples from Table 1. C3 vinylenes/ trisubs/ vinyls/ vinylidene/ Ex# C3 (mol %) (wt %) 1000 C. 1000 C. 1000 C. 1000 C. % vinyl EP-2 25.4 33.8 EP-5 23 30.9 EP-9 23.7 31.8 EP-13 36.6 46.4 EP-14 36.1 45.9 EP-15 33.3 42.8 EP-18 24.0 32.2 EP-25 25.0 33.4 EP-27 25.7 34.2 0 0 0.17 0.01 94 EP-28 21.4 29.0 0.02 0.05 0.14 0.01 64 EP-29 19.5 26.6 0.01 0.02 0.20 0.01 83 EP-30 23.6 31.7 0.01 0.01 0.20 0.01 87 EP-32 20.7 28.1 0 0.02 0.19 0.02 83 EP-37 19.5 26.6 0 0.01 0.34 0.02 92 EP-38 18.9 25.9 0.01 0.03 0.39 0.02 87 EP-39 19.4 26.6 0.01 0.06 0.41 0.02 82 EP-40 23.2 31.2 0 0.01 0.29 0.03 88 EP-41 22.4 30.2 0.02 0.03 0.35 0.03 81 EP-42 22.9 30.8 0.02 0.05 0.39 0.03 80

TABLE 3 GPC 3D data for select EP samples from Table 1. GPC LS GPC LS GPC LS GPC GPC GPC GPC DRI GPC GPC LS Mw Mz Mv LS DRI Mn DRI Mw Mz DRI Ex# Mn (g/mol) (g/mol) (g/mol) Mw/Mn g′ (vis) (g/mol) (g/mol) (g/mol) Mw/Mn EP-2 45,749 75,656 102,109 71,410 1.65 0.973 42,056 83,423 127,169 1.98 EP-5 42,524 64,596 86,719 61,310 1.52 0.978 40,855 69,615 101,323 1.70 EP-9 15,076 22,003 29,224 20,931 1.46 0.959 14,245 24,322 34,970 1.71 EP-13 200,401 485,104 813,916 440,475 2.42 1.106 169,293 494,592 894,116 2.92 EP-14 153,453 319,947 528,962 292,329 2.08 1.071 134,741 335,830 601,817 2.49 EP-15 124,856 228,765 363,099 211,482 1.83 1.012 112,999 240,663 410,141 2.13 EP-18 101,088 173,934 258,316 162,146 1.72 0.976 89,517 86,933 326,829 0.97 EP-25 92,303 154,284 227,004 144,184 1.67 0.970 84,399 167,134 284,644 1.98 EP-27 49,886 83,490 125,542 77,820 1.67 0.920 43,107 87,464 145,405 2.03 EP-28 67,954 117,653 173,671 109,406 1.73 0.940 52,636 130,672 227,052 2.48 EP-29 55,389 96,175 142,735 89,717 1.74 0.956 51,502 103,475 176,723 2.01 EP-30 40,554 68,178 105,771 63,292 1.68 0.939 37,005 71,052 115,499 1.92 EP-32 65,328 119,979 186,254 111,190 1.84 0.963 56,594 123,948 207,881 2.19 EP-37 33,996 57,916 86,755 54,031 1.70 0.943 31,285 60,328 85,248 1.93 EP-38 33,110 51,615 78,644 48,185 1.56 0.924 25,600 54,255 97,298 2.12 EP-39 25,666 45,216 72,856 41,694 1.76 0.940 21,119 47,778 78,324 2.26 EP-40 33,496 52,525 78,351 49,172 1.57 0.918 28,639 55,401 91,127 1.93 EP-41 26,755 46,640 71,332 42,328 1.74 0.927 24,627 48,516 78,716 1.97 EP-42 23,546 40,798 60,714 37,958 1.73 0.921 22,168 14,133 73,735 0.64

TABLE 4 High throughput polypropylene (PP) runs using tri-n-octyl aluminum (TNOAl) or AVTA1. Conditions: For all examples in Table 4, 0.025 μmol of catalyst A was used and activated with 1.1 molar equivalents of dimethylanilinium tetrakis(pentafluorophenyl)borane. Propylene (1.0 ml) was added, and the total reagent and solvent volume in the reactor was 5 ml. All runs utilized 0.05 μmol of bis(diisobutyl aluminum)oxide as scavenger. The run was quenched after 8 psid (Quench Value) of reactor pressure loss. Maximum quench time was set to 30 minutes. AVTA AVTA or Iso- Activity PDI or TnOAl hexane Toluene T quench yield (g P/mmol Mn Mw Mz (Mw/ Tm Ex# TnOAl (umol) (uL) (uL) (° C.) time (s) (g) cat · hr) (g/mol) (g/mol) (g/mol) Mn) (° C.) PP-1 TNOAL 0.251 3728 272 85 159 0.1061 96,091 326,036 599,058 1,327,264 1.84 110.8 PP-2 TNOAL 1.001 3577 422 85 109 0.1071 141,490 94,099 224,867 612,641 2.39 112.3 PP-3 TNOAL 2.001 3377 622 85 106 0.1133 153,917 64,946 146,804 379,705 2.26 112.5 PP-4 TNOAL 0.251 3728 272 100 168 0.0840 72,000 147,585 285,569 612,176 1.93 108.3 PP-5 TNOAL 1.001 3577 422 100 187 0.0965 74,310 69,554 157,043 387,807 2.26 111.7 PP-6 TNOAL 2.001 3377 622 100 193 0.0949 70,806 45,382 97,712 231,172 2.15 109.8 PP-7 TNOAL 2.501 3528 471 85 103 0.1112 155,464 40,672 98,015 269,188 2.41 114.8 PP-8 TNOAL 3.501 3427 571 85 108 0.1091 145,467 32,326 71,934 173,785 2.23 114.8 PP-9 TNOAL 4.001 3377 621 85 146 0.0989 97,545 22,325 57,107 150,074 2.56 115.3 PP-10 TNOAL 2.501 3528 471 100 200 0.0837 60,264 29,255 69,990 196,565 2.39 111.6 PP-11 TNOAL 3.501 3427 571 100 214 0.0763 51,342 18,559 47,071 121,149 2.54 112.5 PP-12 TNOAL 4.001 3377 621 100 261 0.0852 47,007 13,290 45,031 139,094 3.39 110.2 PP-13 AVTA1 0.251 3728 272 85 110 0.1239 162,196 421,928 665,688 1,195,227 1.58 109.8 PP-14 AVTA1 0.501 3678 322 85 107 0.1099 147,903 289,920 513,216 1,006,023 1.77 109.8 PP-15 AVTA1 1.001 3578 422 85 113 0.1112 141,706 163,141 363,919 931,001 2.23 110.5 PP-16 AVTA1 0.251 3728 272 100 285 0.0831 41,987 276,208 434,453 858,574 1.57 107.5 PP-17 AVTA1 0.501 3678 322 100 184 0.0869 68,009 188,589 326,775 691,293 1.73 108.0 PP-18 AVTA1 1.001 3578 422 100 267 0.0844 45,519 139,376 241,141 557,012 1.73 108.8 PP-19 AVTA1 0.251 3728 272 85 109 0.1166 154,040 372,738 665,566 1,504,064 1.79 110.1 PP-20 AVTA1 0.501 3678 322 85 141 0.1093 111,626 305,325 553,453 1,210,448 1.81 110.3 PP-21 AVTA1 1.001 3578 422 85 147 0.1065 104,327 183,136 363,345 842,161 1.98 109.7 PP-22 AVTA1 0.251 3728 272 100 189 0.0876 66,743 250,868 427,830 916,725 1.71 107.4 PP-23 AVTA1 0.501 3678 322 100 158 0.0894 81,478 169,871 340,811 855,226 2.01 108.7 PP-24 AVTA1 1.001 3578 422 100 225 0.0880 56,320 120,925 241,777 592,970 2.00 109.3 PP-25 AVTA1 1.501 3477 522 85 145 0.1016 100,899 114,033 253,279 644,428 2.22 109.2 PP-26 AVTA1 2.001 3377 622 85 129 0.0973 108,614 102,296 238,019 693,801 2.33 111.3 PP-27 AVTA1 2.501 3527 472 85 98 0.1040 152,816 62,613 173,075 585,931 2.76 112.1 PP-28 AVTA1 1.501 3477 522 100 235 0.0852 52,208 98,603 196,899 543,333 2.00 109.5 PP-29 AVTA1 2.001 3377 622 100 239 0.0834 50,249 82,144 159,362 415,328 1.94 109.8 PP-30 AVTA1 2.501 3527 472 100 184 0.0881 68,948 60,406 127,338 334,440 2.11 110.3 PP-31 AVTA1 1.501 3477 522 85 94 0.0882 135,115 137,115 250,275 581,536 1.83 111.5 PP-32 AVTA1 2.001 3377 622 85 143 0.0987 99,390 119,318 228,913 566,669 1.92 111.9 PP-33 AVTA1 1.501 3477 522 100 234 0.0856 52,677 95,389 196,214 529,556 2.06 109.7 PP-34 AVTA1 2.001 3377 622 100 312 0.0775 35,769 85,472 145,777 320,873 1.71 109.5 PP-35 AVTA1 2.501 3527 472 100 195 0.0880 64,985 54,458 128,778 394,184 2.36 111.0 PP-36 AVTA1 3.001 3478 521 85 114 0.0991 125,179 60,872 138,579 372,932 2.28 113.5 PP-37 AVTA1 3.501 3428 571 85 101 0.0995 141,861 58,257 127,761 348,336 2.19 112.8 PP-38 AVTA1 4.001 3377 621 85 100 0.1027 147,888 59,717 128,175 396,107 2.15 111.8 PP-39 AVTA1 3.001 3478 521 100 204 0.0881 62,188 55,202 107,936 255,371 1.96 110.7 PP-40 AVTA1 3.501 3428 571 100 198 0.0836 60,800 46,327 94,344 235,381 2.04 109.5 PP-41 AVTA1 4.001 3377 621 100 210 0.0845 57,943 34,378 82,191 208,755 2.39 108.9 PP-42 AVTA1 3.001 3478 521 85 100 0.0899 129,456 56,289 131,849 351,616 2.34 112.2 PP-43 AVTA1 3.501 3428 571 85 115 0.1010 126,470 75,730 133,774 286,336 1.77 113.5 PP-44 AVTA1 4.001 3377 621 85 121 0.1072 127,577 59,037 127,326 341,903 2.16 112.8 PP-45 AVTA1 3.001 3478 521 100 209 0.0827 56,980 47,563 99,561 236,847 2.09 110.3 PP-46 AVTA1 3.501 3428 571 100 267 0.0806 43,470 38,133 86,432 227,094 2.27 109.7 PP-47 AVTA1 4.001 3377 621 100 246 0.0775 45,366 35,933 77,372 187,787 2.15 109.5

TABLE 5 ¹H NMR data for select PP samples from Table 4. vinylenes/ trisubs/ vinyls/ vinylidenes/ Ex# 1000 C 1000 C 1000 C 1000 C % vinyl PP-2 0.04 0.14 0.09 0.16 21* PP-5 0.04 0.19 0.12 0.20 22  PP-9 0.13 0.49 0.25 0.33 21* PP-12 0.00 0.33 0.23 0.28 27* PP-13 0.07 0.17 0.12 0.23 20  PP-14 0.03 0.09 0.08 0.12 25  PP-15 0.01 0.06 0.07 0.10 29  PP-22 0.05 0.15 0.10 0.17 21  PP-23 0.04 0.09 0.07 0.08 25* PP-24 0.05 0.10 0.09 0.09 27* PP-25 0.01 0.05 0.10 0.09 40* PP-27 0.01 0.03 0.14 0.04 64* PP-29 0.10 0.16 0.35 0.12 48* PP-32 0.01 0.03 0.09 0.04 53* PP-33 0.08 0.11 0.20 0.08 43* PP-35 0.08 0.13 0.32 0.10 51* PP-36 0.00 0.05 0.26 0.05 72* PP-39 0.04 0.05 0.34 0.10 64* PP-40 0.07 0.15 0.53 0.15 59* PP-41 0.09 0.24 1.04 0.26 64* PP-43 0.13 0.29 0.48 0.14 46* PP-44 0.02 0.05 0.24 0.04 69* *indicates that the ¹H NMR baseline was noisy.

TABLE 6 High throughput polyethylene (PE) and ethylene-octene (EO) runs using tri-n-octyl aluminum (TNOAl), AVTA2 or AVTA3. Conditions: For all examples in Table 46, 0.020 μmol of catalyst A or B was used and activated with 1.1 molar equivalents of dimethylanilinium tetrakis(pentafluorophenyl)borane. 1-octene (50 μmol) was added for EO polymerizations, and the total reagent and solvent volume in the reactor was 5 ml. All runs utilized 0.05 μmol of bis(diisobutyl aluminum)oxide as scavenger. The run was quenched after 20 psid (Quench Value) of ethylene uptake. Maximum quench time was set to 30 minutes. Activity Iso- Tol- (g PDI AVTA hexane uene quench T yield P/mmol Mn Mw Mz (Mw/ C8 Tm Ex# TMC AVTA (umol) (uL) (uL) time (s) (° C.) (g) cat · hr) (g/mol) (g/mol) (g/mol) Mn) (wt %) (° C.) EO-1 A AVTA3 0.501 4731 219 153 85 0.1220 143,529 361,321 907,576 3,376,196 2.51 17.9 107.4 PE-1 A AVTA3 2.501 4381 618 23 85 0.0909 711,391 65,067 106,506 217,566 1.64 0 134.1 PE-2 A AVTA2 2.501 4381 618 37 85 0.1048 509,838 120,654 228,556 595,358 1.89 0 132.6 EO-2 A AVTA3 0.501 4731 219 186 100 0.1113 107,710 285,786 500,423 1,172,199 1.75 20.7 101.2 PE-3 A AVTA3 2.501 4381 618 21 100 0.0676 579,429 45,404 72,290 154,618 1.59 0 132.5 PE-4 A AVTA2 2.501 4381 618 21 100 0.0898 769,714 83,185 144,060 309,560 1.73 0 132.4 EO-3 A AVTA3 1.001 4631 318 153 85 0.1205 141,765 184,321 338,318 828,837 1.84 18.1 105.0 EO-4 A AVTA3 1.501 4531 418 37 85 0.1180 574,054 121,905 222,546 574,863 1.83 14.1 106.7 EO-5 A AVTA2 1.501 4531 418 99 85 0.1196 217,455 179,452 321,463 745,551 1.79 19.9 106.2 EO-6 A AVTA3 1.001 4631 318 32 100 0.0910 511,875 131,426 205,789 428,507 1.57 14.6 101.5 EO-7 A AVTA3 1.501 4531 418 23 100 0.0810 633,913 76,659 120,969 244,923 1.58 12.6 105.3 EO-8 A AVTA2 1.501 4531 418 30 100 0.0976 585,600 119,755 209,324 494,755 1.75 12.9 100.9 EO-9 A AVTA2 0.501 4731 219 164 85 0.1187 130,280 393,699 772,879 2,067,033 1.96 20.4 105.0 EO-10 A AVTA3 2.001 4431 518 25 85 0.1014 730,080 86,466 134,196 268,756 1.55 10.9 110.6 EO-11 A AVTA2 2.001 4431 518 38 85 0.1174 556,105 133,985 248,579 621,633 1.86 16.3 106.2 EO-12 A AVTA2 0.501 4731 219 56 100 0.0918 295,071 273,603 496,511 1,167,847 1.81 18.5 97.9 EO-13 A AVTA3 2.001 4431 518 24 100 0.0712 534,000 54,064 87,965 194,251 1.63 11.4 111.4 EO-14 A AVTA2 2.001 4431 518 27 100 0.0969 646,000 95,278 166,714 426,502 1.75 13.2 104.5 EO-15 A AVTA2 1.001 4631 319 113 85 0.1169 186,212 235,798 437,689 985,772 1.86 18.6 105.9 EO-16 A AVTA3 2.501 4331 618 24 85 0.0828 621,000 56,758 96,651 196,361 1.70 8.1 116.4 EO-17 A AVTA2 2.501 4331 618 24 85 0.1106 829,500 97,090 167,251 363,833 1.72 14.5 108.1 EO-18 A AVTA2 1.001 4631 319 40 100 0.0918 413,100 165,756 298,665 737,468 1.80 18.3 101.5 EO-19 A AVTA3 2.501 4331 618 22 100 0.0687 562,091 49,197 72,635 138,884 1.48 5.6 117.3 EO-20 A AVTA2 2.501 4331 618 21 100 0.0864 740,571 73,119 124,550 352,065 1.70 10.3 109.2 EO-21 B AVTA3 0.501 4731 219 77 85 0.0564 131,844 294,032 497,283 1,000,672 1.69 8.9 113.2 PE-5 B AVTA3 2.501 4381 618 22 85 0.0850 695,455 71,836 128,242 277,907 1.79 0 133.8 PE-6 B AVTA2 2.501 4381 618 25 85 0.0963 693,360 119,738 258,807 694,257 2.16 0 131.9 EO-22 B AVTA3 0.501 4731 219 43 100 0.0959 401,442 277,805 502,086 1,207,864 1.81 15.7 103.1 PE-7 B AVTA3 2.501 4381 618 22 100 0.0679 555,545 53,053 87,222 176,276 1.64 0 132.7 PE-8 B AVTA2 2.501 4381 618 22 100 0.0845 691,364 78,787 153,194 377,095 1.94 0 132.2 EO-23 B AVTA3 1.001 4631 318 44 85 0.1045 427,500 191,683 357,743 786,227 1.87 12.3 107.9 EO-24 B AVTA3 1.501 4531 418 29 85 0.0749 464,897 112,541 185,327 392,724 1.65 7.9 113.4 EO-25 B AVTA2 1.501 4531 418 34 85 0.0989 523,588 190,387 342,189 743,452 1.80 11.6 109.6 EO-26 B AVTA3 1.001 4631 318 34 100 0.0761 402,882 130,891 212,894 476,552 1.63 9.6 109.7 EO-27 B AVTA3 1.501 4531 418 26 100 0.0830 574,615 95,662 163,687 383,864 1.71 8.6 112.3 EO-28 B AVTA2 1.501 4531 418 32 100 0.0881 495,563 129,555 231,671 540,891 1.79 9.3 109.8 EO-29 B AVTA2 0.501 4731 219 115 85 0.0954 149,322 483,002 890,657 2,223,574 1.84 14.1 107.4 EO-30 B AVTA3 2.001 4431 518 30 85 0.0654 392,400 77,063 137,500 307,605 1.78 5.9 118.6 EO-31 B AVTA2 2.001 4431 518 28 85 0.1011 649,929 144,858 267,417 637,823 1.85 11.6 110.5 EO-32 B AVTA2 0.501 4731 219 35 100 0.0892 458,743 324,062 615,865 1,383,659 1.90 15.2 104.8 EO-33 B AVTA3 2.001 4431 518 23 100 0.0776 607,304 69,660 120,856 264,994 1.73 4.2 122.5 EO-34 B AVTA2 2.001 4431 518 32 100 0.0685 385,313 74,522 146,160 376,116 1.96 5.8 119.9 EO-35 B AVTA2 1.001 4631 319 38 85 0.0862 408,316 254,934 438,047 960,665 1.72 8.1 112.2 EO-36 B AVTA3 2.501 4331 618 41 85 0.0551 241,902 73,850 115,997 253,515 1.57 4.6 121.6 EO-37 B AVTA2 2.501 4331 618 27 85 0.0980 653,333 126,895 241,187 571,676 1.90 9.3 113.4 EO-38 B AVTA2 1.001 4631 319 35 100 0.0819 421,200 152,389 307,178 724,831 2.02 11.7 109.3 EO-39 B AVTA3 2.501 4331 618 20 100 0.0680 612,000 46,839 81,397 165,173 1.74 3.6* 123.6 EO-40 B AVTA2 2.501 4331 618 22 100 0.0882 721,636 81,212 162,758 433,899 2.00 8.6 113.5 *octene content by FTIR is outside of the calibration range

Unless otherwise indicated, proton NMR spectra are collected using a 400 MHz Varian pulsed fourier transform NMR spectrometer equipped with a variable temperature proton detection probe operating at 120° C. The polymer sample is dissolved in 1,1,2,2-tetrachloroethane-d2 (TCE-d2) and transferred into a 5 mm glass NMR tube. Typical acquisition parameters are sweep width=10 KHz, pulse width=30 degrees, acquisition time=2 s, acquisition delay=5 s and number of scans=120. Chemical shifts are determined relative to the TCE-d2 signal which is set to 5.98 ppm.

The chain end unsaturations are determined as follows. The vinyl resonances of interest are between from about 5.0 to 5.1 ppm (VRA), the vinylidene resonances between from about 4.65 to 4.85 ppm (VDRA), the vinylene resonances from about 5.31 to 5.55 ppm (VYRA), the tri-substituted unsaturated species from about 5.11 to 5.30 ppm (TSRA) and the aliphatic region of interest between from about 0 to 2.1 ppm (IA). The number of vinyl groups/1000 Carbons is determined from the formula: (VRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA). Likewise, the number of vinylidene groups/1000 Carbons is determined from the formula: (VDRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA), the number of vinylene groups/1000 Carbons from the formula (VYRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA) and the number of tri-substituted groups from the formula (TSRA*1000)/((IA+VRA+VYRA+VDRA)/2)+TSRA). VRA, VDRA, VYRA, TSRA and IA are the integrated normalized signal intensities in the chemical shift regions defined above.

GPC3D: Unless otherwise indicated, molecular weight (weight-average molecular weight, M_(w), number-average molecular weight, M_(n), and molecular weight distribution, M_(w)/M_(n) or MWD, and branching index (g′vis)) are determined using a High Temperature Size Exclusion Chromatograph (either from Waters Corporation or Polymer Laboratories), equipped with a differential refractive index detector (DRI), an online light scattering (LS) detector, and a viscometer. Experimental details not described below, including how the detectors are calibrated, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, 6812-6820, (2001).

Three Polymer Laboratories PLgel 10 mm Mixed-B columns are used. The nominal flow rate was 0.5 cm³/min, and the nominal injection volume is 300 μL. The various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at 135° C. Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. The TCB is then degassed with an online degasser before entering the SEC. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160° C. with continuous agitation for about 2 hours. All quantities are measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.324 g/ml at 135° C. The injection concentration ranges from 1.0 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8-9 hours before injecting the first sample. The LS laser is turned on 1 to 1.5 hours before running samples.

The concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, I_(DRI), using the following equation: c=K _(DRI) I _(DRI)/(dn/dc) where K_(DRI) is a constant determined by calibrating the DRI, and (dn/dc) is the same as described below for the light scattering (LS) analysis. Units on parameters throughout this description of the SEC method are such that concentration is expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity is expressed in dL/g.

The light scattering detector used is a Wyatt Technology High Temperature mini-DAWN. The polymer molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press 1971):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the DRI analysis, A₂ is the second virial coefficient [for purposes of this invention and the claims thereto, A₂=0.0006 for propylene polymers and 0.001 otherwise], P(θ) is the form factor for a monodisperse random coil (M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971), and K_(o) is the optical constant for the system:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{dn}/{dc}} \right)}^{2}}{\lambda^{4}N_{A}}$ in which N_(A) is Avogadro's number, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 135° C. and X=690 nm. For purposes of this invention and the claims thereto (dn/dc)=0.104 for propylene polymers and 0.1 otherwise.

A high temperature Viscotek Corporation viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, η_(s), for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the following equation: η_(s) =c[η]+0.3(c[η])² where c is concentration and is determined from the DRI output.

The branching index, g′ (also referred to as g′vis), is calculated using the output of the SEC-DRI-LS-VIS method as follows. The average intrinsic viscosity, [η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\Sigma\;{c_{i}\lbrack\eta\rbrack}_{i}}{\Sigma\; c_{i}}$ where the summations are over the chromatographic slices, i, between the integration limits.

The branching index g′vis is defined as:

$g^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{k\; M_{v}^{\alpha}}$ where, for purpose of this invention and claims thereto, α=0.695 for ethylene, propylene, and butene polymers; and k=0.000579 for ethylene polymers, k=0.000262 for propylene polymers, and k=0.000181 for butene polymers. My is the viscosity-average molecular weight based on molecular weights determined by LS analysis.

All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is allowed, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa. 

What is claimed is:
 1. A catalyst system comprising a quinolinyldiamido transition metal complex represented by the Formula I:

wherein: M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal; J is a three-atom-length bridge between the quinoline and the amido nitrogen; X is an anionic leaving group; L is a neutral Lewis base; R¹ and R¹³ are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups; R², R³, R⁴, R⁵, and R⁶ are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino; n is 1 or 2; m is 0, 1, or 2 n+m is not greater than 4; and any two adjacent R groups (e.g., R¹ & R², R² & R³, etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; any two X groups may be joined together to form a dianionic group; any two L groups may be joined together to form a bidentate Lewis base; and an X group may be joined to an L group to form a monoanionic bidentate group; an activator; and and a metal hydrocarbenyl transfer agent.
 2. The catalyst system of claim 1, wherein J is selected from the following structures:

where

indicates connection to the complex.
 3. The catalyst system of claim 1, wherein the complex is further represented by Formula (II):

wherein M, L, X, m, n, R², R³, R⁴, R⁵, R⁶, and R¹³ are as defined in claim 1, and E is carbon, silicon, or germanium; R⁷ through R¹² are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and any two adjacent R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.
 4. The catalyst system of claim 3, wherein R¹¹ and R¹² are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl.
 5. The catalyst system of claim 3, wherein E is carbon.
 6. The catalyst system of claim 3, wherein R⁷, R⁸, R⁹, and R¹⁰ are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, and trimethylsilyl.
 7. The catalyst system of claim 1, wherein M is Ti, Zr, or Hf.
 8. The catalyst system of claim 1, wherein R², R³, R⁴, R⁵, and R⁶ are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.
 9. The catalyst system of claim 1, wherein each L is independently selected from Et₂O, MeOtBu, Et₃N, PhNMe₂, MePh₂N, tetrahydrofuran, and dimethylsulfide and each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.
 10. The catalyst system of claim 1, wherein R¹ is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl; and/or R¹³ is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.
 11. The catalyst system of claim 1, wherein J is dihydro-1H-indenyl and R¹ is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.
 12. The catalyst system of claim 1, wherein R¹ is 2,6-diisopropylphenyl and R¹³ is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.
 13. The catalyst system of claim 1, wherein the activator comprises an alumoxane and/or a non-coordinating anion.
 14. The catalyst system of claim 1, wherein the activator comprises one or more of: trimethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄ ⁻], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, triphenylcarbenium tetraphenylborate, and triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate.
 15. The catalyst system of claim 1, wherein the metal hydrocarbenyl transfer agent is represented by the formula: Al(R′)_(3-v)(R″)_(v) wherein each R′, independently, is a C₁-C₃₀ hydrocarbyl group; each R″, independently, is a C₄-C₂₀ hydrocarbenyl group having an allyl chain end; and v is from 0.01 to
 3. 16. The catalyst system of claim 15, wherein R″ is butenyl, pentenyl, hexenyl, heptenyl, octenyl or decenyl, and/or R′ is methyl, ethyl, propyl, isobutyl, or butyl.
 17. The catalyst system of claim 1, wherein the metal hydrocarbenyl transfer agent comprises one or more of tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, dimethyl(dec-9-en-1-yl)aluminum, diethyl(dec-9-en-1-yl)aluminum, dibutyl(dec-9-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, and diisobutyl(dodec-11-en-1-yl)aluminum.
 18. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of claim
 1. 19. The process of claim 18, wherein the monomer comprises ethylene or propylene.
 20. The process of claim 18, wherein the monomers comprise at least two of ethylene, propylene, and an alkyl diene.
 21. The process of claim 18, wherein the transition metal complex is supported.
 22. The process of claim 21, wherein the support is silica.
 23. The process of claim 18, wherein the polymerization is performed in one or more continuous stirred tank reactors in series or in parallel.
 24. The process of claim 18, wherein the monomer comprises ethylene and octene.
 25. The process of claim 18, wherein the monomer comprises ethylene.
 26. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of claim
 3. 27. The catalyst system of claim 1, wherein the metal hydrocarbenyl transfer agent is represented by the formula: Al(R′)_(3-v)(R″)_(v) wherein each R′, independently, is a C₁-C₃₀ hydrocarbyl group; each R″, independently, is a C₄-C₂₀ hydrocarbenyl group having an allyl chain end; and v=2.
 28. The catalyst system of claim 15, wherein R″ is butenyl, pentenyl, hexenyl, heptenyl, octenyl or decenyl, and R′ is methyl, ethyl, propyl, isobutyl, or butyl. 